Glycosidic derivatives

ABSTRACT

O-glycosidic compounds useful for therapy or prophylaxis of a wide variety of diseases, for diagnostic use or as research chemicals. Another object of the present invention is to provide a method for preparing the O-glycosidic compounds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel glycosides and glycoconjugatesuseful as i.a. synthetic biological receptors.

2. Description of the Prior Art

Natural glycoconjugates consist of a carbohydrate portion, which is, inmost cases, coupled to a lipid or a protein (cf. Hakomori (1981) andSharon & Lis (1981)). In most of the glycolipids, the sugar is coupledto either the fatty amino alcohol sphingosine or to glycerol, which inturn are transformed into fatty acid derivatives. The general structuresof these two types of glycolipids are shown below.

    __________________________________________________________________________                                                         NATURAL                                                                       GLYCOLIPIDS              __________________________________________________________________________     ##STR1##                                            GLYCOSPHINGO- LIPID       ##STR2##                                            GLYCOGLYCERO-            __________________________________________________________________________                                                         LIPID                

In the glycoproteins, the sugar moiety is coupled directly onto an aminoacid in a protein. Glycolipids and glycoproteins are integral parts ofthe plasma membranes of mammalian cells. Some of these glycoconjugatesfunction i.a. as specific receptors towards a variety of biologicalentities. The carbohydrate part of the glycoconjugate is exposed on theoutside of the plasma membrane, and it may consequently exhibitantigenic properties. This is the basis for the various blood-groupsystems (cf. Lemieux (1978)). It has recently been shown thatmembrane-carbohydrates of the above type are important as receptors forproteins (cf. Sharon & Lis (1972) and Kabat (1980)) like lectines,antibodies and hormones and for anchoring microorganisms to cellsurfaces (cf. Beachey (1981)).

Unnatural glycoconjugates (so-called neo-glycoconjugates) have beenprepared both as neo-glycolipids (cf. Slama & Rando (1980) and Dahmen etal. (Carbohydr. Res., 127, 1984)) and neo-glycoproteins (cf. Lemieux etal. (1975) and Dahmen et al. (Carbohydr. Res., 129, 1984)). Noneo-glycolipids having a close molecular similarity to the naturalcompound have, however, yet been prepared. It is known (cf.Israelachvili et al. (1980)) that the chemical structure of thehydrophobic part of lipids determines the type of aggregates that can beformed (micelles, liposomes, etc.) and also the kind of influence that alipid will have when it is incorporated into e.g. a cellular membrane.In view of the high receptor specificity and biological importance ofcarbohydrate complexes it is obvious that there is a great need formolecularly well defined, easily prepared glycoconjugates for use intherapy, prophylaxis, and diagnosis as well as in biochemical research.

SUMMARY OF THE INVENTION

One object of the present invention is to provide novel O-glycosidiccompounds useful for therapy or prophylaxis of a wide variety ofdiseases, for diagnostic use or as research chemicals.

Another object of the present invention is to provide a method forpreparing the novel O-glycosidic compounds.

Thus, the invention relates to O-glycosidic compounds of the formula I##STR3## wherein

n is an integer from 1 to 10, inclusive, and Sugar is selected from thegroup consisting of D-glucose, D-galactose, D-mannose, D-xylose,D-ribose, D-arabinose, L-fucose, 2-acetamido-2-deoxy-D-glucose,2-acetamido-2-deoxy-D-galactose, D-glucuronic acid, D-galacturonic acid,D-mannuronic acid, 2-deoxy-2-phthalimido-D-glucose,2-deoxy-2-phthalimido-D-galactose and sialic acid, and derivativesthereof whereby, when n>1, the Sugar units may be the same or different;and

R₃ is H and

R₁ and R₂ which may be the same or different are

a group CH₂ X, wherein X is a leaving group,

a group of the formula II ##STR4## wherein m and p independently are 0or 1 and m+p is 0, 1 or 2,

R₄ is a saturated or unsaturated, branched or unbranched alkyl chain of1-25 carbon atoms, aryl or a steroid group, and

R₅ is H, CHO, NO₂, NH₂, OH, SH, COOH, COOR₁₀ wherein R₁₀ is C₁₋₄ -alkylor a carrier, CONHNH₂, CON₃, CH(OR₁₀)₂ wherein R₁₀ is as defined above,or a carrier,

a group of the formula III

    --CH.sub.2 --O--R.sub.6                                    III

wherein

R₆ is H or the group --R₄ --R₅, wherein R₄ and R₅ are as defined above,

or a group of the formula IIIa ##STR5## wherein R₇ and R'₇, which may bethe same or different, are the same as R₆ defined above; or

R₂ and R₃ together form ═CH₂, and

R₁ is

CH₂ X, wherein X is as defined above,

a group of the formula II defined above, wherein R₄, R₅, m and p are asdefined above,

a group of the formula III defined above, wherein R₆ is as definedabove,

a group of the formula IIIa defined above, wherein R₇ and R'₇ are asdefined above,

or a group of the formula IV

    --CH.sub.2 --R.sub.8                                       IV

wherein

R₈ is a carrier; as well as polymers formed from monomers of the formulaI, the polymers having

(1) the formula XX ##STR6## wherein Sugar, n, and R₄ are as definedabove, and k is an integer from 2 to 1000; or

(2) the formula XXI ##STR7## wherein Sugar, n, k, and R₄ are as definedabove.

In the formula I, the carbohydrate moiety "(Sugar)_(n) " is attached tothe rest of the molecular through an α-or β-bond to the 1-carbon atom(the anomeric carbon) in one of the Sugar units. The carbohydrate unit,to which the rest of the molecule is bonded, is usually the terminalcarbohydrate unit at the reducing end of an unbranched or branched chainof pentose or hexose units.

It will be seen that the monomers covered by Formula I includeO-glycosidic compounds of the formula ##STR8## B_(x) (R₁) and B_(y)(R₂), which may be the same, or different, are groups of the formula II,##STR9## and where "sugar," n, m, p, R₄ and R₅ are as defined above.

The compounds set forth in Tables 2, 3, 4 and 5 below all fall within Ixas set forth above.

In the present context, the term "or derivatives thereof" with referenceto the Sugar units designates that some or all of the free hydroxygroups in the carbohydrate moiety are derivatised or replaced by suchgroups as alkyl (such as methyl, ethyl or propyl), amino, fluoro orother groups. Such groups may in turn be substituted with variousfunctional groups. The hydroxy groups in the sugar ring may bederivatised with acyl such as acetyl or benzyl, C₁₋₄ lower alkyl (inparticular methyl or ethyl), or tetrahydropyranyl as well as a widevariety of other groups. Such derivative groups are capable of changingthe properties (e.g. hydrophilicity, hydrophobicity, polarity, overallshape, etc.) of the carbohydrate moiety.

In the present context, the term "leaving group" designates any groupthat is easily split off when the carbon atom, to which it is attached,is subjected to a nucleophilic attack. Typical examples of leavinggroups are halogens such as chlorine, bromine and iodine, in particularbromine, p-toluenesulfonyl, mesyl, as well as ester functions such aslower alkyl ester functions, e.g. methylcarbonyloxy, ethylcarbonyloxy,propylcarbonyloxy, etc., and aryl ester functions such as phenylcarbonyloxy, wherein the phenyl group may also carry substituents.

The term "carrier" for R₅ designates any organic or inorganic, polymericor macromolecular structure to which the aglycon part of theO-glycosidic compound of the formula I is attached. Examples of suchcarriers are residues of proteins, polysaccharides, plastic polymers andinorganic materials. Residues of proteins are preferably bonded throughnucleophilic groups in the proteins, e.g. such groups as amino, hydroxyand mercapto groups. The proteins themselves may be any of a widevariety of proteins, in particular biologically compatible proteins suchas globulins, albumins such as bovine serum albumin, fibrins, polylysin,"key-hole" limpet hemocyanine (KLH), etc. The polysaccharides, to whichthe O-glycosidic compounds are attached, may be any of a wide variety ofpolysaccharides. The aglycon part of the compound of formula I may bebonded through hydroxy groups on ordinary polysaccharides such ascellulose, starch or glycogen, through amino groups on amino saccharidessuch as chitosan or aminated sepharose, and through mercapto groups ofthio-modified polysaccharides. Examples of plastics to which the aglyconpart of the compounds of the formula I may be attached are aminatedlatex, thiolated, aminated, or hydroxylated polystyrene, and polyvinylalcohol. The plastics in question may be in the form of e.g. beads orfilm. Examples of inorganic material, to which the aglycon part of thecompounds of the formula I may be attached are silicon oxide materialssuch as silica gel, zeolite, diatomaceous earth, or the surface ofvarious glass or silicagel types such as thiolated or aminated glass,where the silica gel or the glass may be in the form of e.g. beads.Another example of an inorganic material is aluminium oxide.

Examples of saturated or unsaturated, branched or unbranched alkylchains of 1-25 carbon atoms for R₄ are methylene, dimethylene,tetramethylene, octamethylene, hexadecanmethylene, octadecanmethyleneand octadec-9-enylene, preferably unbranched saturated alkyl chains suchas octamethylene, hexadecamethylene, and octadecamethylene when R₅ is H.Preferred groups --R₄ --R₅, when R₅ is different from H. are (CH₂)₂--COOR₁₀ and (CH₂)₁₀ --COOR₁₀, where R₁₀ is as defined above. Examplesof the group --R₄ -R₅, where R₄ is aryl, is a phenyl group carrying assubstituent any of the groups R₅ defined above and in any of theavailable positions.

The term "steroid group" may designate any commonly occurring biologicalsteroid group such as the types of steroids, which, themselves or theform of derivatives thereof, are incorporated into biological membranes.Examples of such steroid units are cholesterol and lanosterol.

Examples of C₁₋₄ alkyl are methyl, ethyl, propyl, i-propyl, n-butyl,i-butyl and tert.butyl.

The polymers of the formula XX form a linear polymer in that thecarbohydrate moiety with the 4-carbon aglycon unit attached alternateswith a dithio unit in the fashion of a copolymer.

The polymers of the formula XXI are composed in a similar manner in thatthe carbohydrate moiety with the 4-carbon aglycon unit attachedalternates in a copolymer manner with a trithio unit. Since the 4-carbonaglycon unit has only two bonding sites whereas the trithio unit hasthree bonding sites, the resulting structure is a 3-dimensional networkin which a bonding site of the 4-carbon aglycon unit is always bonded tothe sulphur atom of a trithio unit, whereas the 4-carbon aglycon unit isnever bonded to another 4-carbon unit, and a trithio unit is neverbonded to another trithio unit. This complicated spatial relationship isindicated through the vertical wavy line in the formula XXI.

DETAILED DESCRIPTION OF THE INVENTION

With respect to the compounds of the formula I in which R₃ is H, thosein which R₁ and R₂ are identical are attractive since they are simplerto prepare than those in which R₁ and R₂ are non-identical. However,compounds in which R₁ and R₂ are dissimilar have a greater potential forhaving a wider spectrum of functionalities combined in a singlecompound, thereby rendering such compounds able to function inadditional ways, e.g. in biological system.

Among compounds in wnich R₁ and R₂ are identical, preferred compoundsare those in which R₁ and R₂ are CH₂ X, wherein X is halogen,alkylcarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy or arylsulfonyloxy.The alkyl moieties are preferably C₁₋₄ alkyl, and the aryl moiety ispreferably an optionally substituted phenyl group, in particular tolyl.A preferred halogen is Br.

Another preferred class of compounds in which R₁ and R₂ are identicalare compounds in which R₁ and R₂ are a group of formula II, wherein mand p are as defined above, R₄ is an unbranched alkyl chain of 2-17carbon atoms, and R₅ is CH₃, COOCH₃ or a carrier. Examples of unbranchedalkyl chains of 2-17 carbon atoms are dimethylene, heptamethylene,decamethylene, pentadecamethylene, and heptadecamethylene. In aparticularly preferred subclass of compounds, m+p is 0 or 2.

Among the compounds in which R₁ and R₂ are different, interestingcompounds are those in which one of R₁ and R₂ contains a long-chainhydrocarbon moiety terminated by a hydrocarbon chain, optionally with ashorter chain length than the first substituent.

Among the compounds in which R₂ and R₃ together form ═CH₂ a preferredclass of compounds are those in which R₁ is CH₂ X, wherein X is halogen,alkylcarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy or arylsulfonylox. Xis preferably Br.

Another preferred class of compounds in which R₂ and R₃ together form═CH₂ are those in which R₁ is a group of the formula II defined above,wherein R₄ is an unbranched alkyl chain of 2-17 carbon atoms, R₅ is CH₃,COOCH₃ or a carrier, and m+p is 0.

A further preferred subclass of compounds in which R₂ and R₃ togetherform ═CH₂ are those in which R₁ is a group of the formula III definedabove, wherein R₆ is a group --R₄ --R₅, wherein R₄ is an unbranchedalkyl chain of 2-17 carbon atoms, R₅ is CH₃, COOCH₃ or a carrier.

Yet another preferred class of compounds in which R₂ and R₃ togetherform ═CH₂ are those in which R₁ is a group of a formula IIIa, wherein R₇and R'₇ are identical and are unbranched alkyl chains of 8-18 carbonatoms, e.g. octyl, hexadecyl or octadecyl.

Examples of important carbohydrate moieties (Sugar)_(n) are listedbelow. In the list the various saccharide units are written according tothe commonly used short-hand within the field in which the bondingbetween each saccharide unit (given as an abbreviation) is specifiedwith respect to between which carbon atom in either saccharide unit thebond exists, and whether the bond is in an α-or β-configuration. Thedesignation "NAc" or "NPhth" means that the saccharide unit in questioncarries an acetylamino or a phthalimido group, respectively, in the2-position. The symbol "A" means the corresponding acid. Thus, "GlcA" isglucuronic acid. The notation "3Me" means that the hydroxyl groupnormally present in the 3-position has been replaced by a methyl group.Analogously, "3CH₂ OH" refers to a hydroxymethyl group. Although thesaccharide units may be present in both furanosidic and pyranosidicforms, pyranosidic units are normally preferred.

Examples of the carbohydrate moieties are:

Gal

Glc

Man

Fuc

Xyl

Rib

Ara

GlcNAc

GalNAc

GlcA

GalA

ManA

GlcNPhth

GalNPhth

NeuNAc

Manα1→3Man

Manα1→2Man

Manα1→6Man

Manβ1→4GlcNAc

Galβ1→4GlcNAc

GlcNAcβ1→4Man

GlcNAcβ1→2Man

Galβ1→6GlcNAc

Fucα1→6GlcNAc

Manα1→6GlcNAc

Galβ1→2Man

Fucα1→3GlcNAc

Fucα1→2Gal

Fucα1→3Gal

Fucα1→6Gal

Galβ1→3GlcNAc

Galβ1→2Gal

Galβ1→6Gal

Galβ1→3Gal

GalNAcα1→3Gal

GlcNAcβ1→3Gal

Galβ1→4Glc

Galα1→4Gal

GalNAcβ1→3Gal

GalNAcα1→3GalNAc

GalNAcβ1→4Gal

Galβ1→3GalNAc

Galα1→3Gal

Glcα1→6Glcα1→4Glcα1→4Glc

Glcα1→4Glc

Glcβ1→4Glc

NeuNAcα2→3Gal

NeuNAcα2→6Gal

NeuNAcα2→3GalNAc

NeuNAcα2→6GlcNAc

NeuNAcα2→8NeuNAc

Glcβ1→4Glcβ1→4Glc

Glcα1→4Glcα1→4Glc

Manα1→3(Manα1→6)Man

Galβ1→3GalNAcβ1→4Galβ1-4Glc

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4Glc

GalNAcβ1→3Galα1→4Galβ1→4Glc

GalNAcβ1→3Galα1→3Galβ1→4Glc

Galβ1→4GlcNAcβ1→3Galβ1→4Glc

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4Glc

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.3Galβ1→4Glc ##STR10##Galβ1→3Galβ1→4Glc Galβ1→3Galβ1→3Galβ1→4Glc

GlcNAcβ1→3Gal

Galβ1→4Glc3Me

Galα1→4Gal3Me

Galβ1→4Glc3CH₂ OH

Galα1→4Gal3CH₂ OH

Galα1→4Galβ1→4Glc

Galα1→4Galβ1→4GlcNAc

Glcα1→6Glcα1→4Glc

Examples of important aglycon moieties are:

CH₂ --CH--[CH₂ S--(CH₂)₁₅)--CH₃ ]₂

CH--CH--[CH₂ S--(CH₂)₈ --CH.sub.═^(z) CH--(CH₂)₇ --CH₃ ]₂

CH₂ --CH--[CH₂ --S--(CH₂)₂ --COOCH₃ ]₂

CH₂ --CH--[CH₂ --S--(CH₂)₁₀ --COOCH₃ ]₂

CH₂ --CH--[CH₂ --S--(CH₂)₆ --NH₂ ]₂

CH₂ --CH--[CH₂ --SO--(CH₂)₁₅ --CH₃ ]₂

CH₂ --CH--[CH₂ --SO--(CH₂)₈ --CH.sub.═^(z) CH--(CH₂)₇ --CH₃ ]₂

CH₂ --CH--[CH₂ --SO--(CH₂)₂ --COOCH₃ ]₂

CH₂ --CH--[CH₂ --SO--(CH₂)₁₀ --COOCH₃ ]₂

CH₂ --CH--[CH₂ --SO--(CH₂)₆ --NH₂ ]₂

--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

--CH₂ --CH(CH₂ --SO₂ --(CH₂)₈ --CH.sub.═^(z) CH--(CH₂)₇ --CH₃)₂

--CH₂ --CH(CH₂ --SO₂ --(CH₂)₂ --COOCH₃)₂

--CH₂ --CH(CH₂ (SO₂ --(CH₂)₁₀ --COOCH₃)₂

--CH₂ --CH(CH₂ --SO₂ --(CH₂)₆ --NH₂)₂

--CH₂ C(═CH₂)--CH₂ --S--(CH₂)₁₅ --CH₃

--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₆ --NH₂

--CH₂ --C(═CH₂)--CH₂ --N--((CH₂)₁₅ --CH₃)₂

--CH₂ --C(═CH₂)--CH₂ --O--Cholesteryl

CH₂ --CH--[CH₂ --S--(CH₂)₁₀ --COOCH₃ ]CH₂ --S--(CH₂)₇ CH₃

CH₂ --CH--[CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃ ]CH₂ --S--(CH₂)₇ --CH₃

CH₂ --CH--[CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃ ]CH₂ --SO₂ --(CH₂)₇ --CH₃

--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

--CH₂ --CH(CH₂ --SO₂ --(CH₂)₂ --COOH)₂

It is to be understood, that each and every one of the above-mentionedcarbohydrate moieties may be combined with each and every one of theabove-mentioned aglycon moieties, and that the listing should beunderstood as a practical way of representing each and every one of theresulting glycosidic compounds.

Examples of preferred glycosidic compounds of the formula I are:

GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

FucO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

FucO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

FucO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

FucO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

FucO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

FucO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

XylO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

XylO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

XylO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

XylO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

XylO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

XylO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

RibO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

RibO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

RibO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

RibO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

RibO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

RibO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

AraO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

AraO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

AraO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

AraO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

AraO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

AraO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

GalNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcAO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcAO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GlcAO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalAO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalAO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalAO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GalAO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

ManAO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

ManAO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

ManAO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

ManAO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

ManAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

ManAO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcNPhthO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNPhthO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNPhthO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

GlcNPhthO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNPhthO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNPhthO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNPhthO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNPhthO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNPhthO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

GalNPhthO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNPhthO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNPhthO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

NeuNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

NeuNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

NeuNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcO--CH₂ --C(═CH₂ --CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manα1→3ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manα1→3ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manα1→3ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Manα1→3ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Manα1→3ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manα1→3ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manα1→2ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manα1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manα1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Manα1→2ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Manα1→2ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manα1→2ManO--CH₂ --(C═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manα1→6ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manα1→6ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manα1→6ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Manα1→6ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Manα1→6ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manα1→6ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manβ1→4GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Manβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Manβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcNAcβ1→4ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→4ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→4ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GlcNAcβ1→4ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNAcβ1→4ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNAcβ1→4ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcNAcβ1→2ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GlcNAcβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNAcβ1→2ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNAcβ1→2ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→6GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galβ1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Fucα1→6GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Fucα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Fucα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Fucα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --C₃)₂

Fucα1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Fucα1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manα1→6GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Manα1→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Manα1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manα1→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→2ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galβ1→2ManO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→2ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→2ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Fucα1→3GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Fucα1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Fucα1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Fucα1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Fucα1→3GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Fucα1→3GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Fucα1→2GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Fucα1→2GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Fucα1→2GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Fucα1→2GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Fucα1→2GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Fucα1→2GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Fucα1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Fucα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Fucα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Fucα1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Fucα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Fucα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Fucα1→6GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Fucα1→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Fucα1→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Fucα1→6GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Fucα1→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Fucα1→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galβ1→3GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→2GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→2GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→2GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galβ1→2GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→2GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→2GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→6GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galβ1→6GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcα1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GalNAcα1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galα1→4GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galα1→4GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galα1→4GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galα1→4GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galα1→4GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→4GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcβ1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GalNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcα1→3GalNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcα1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcα1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GalNAcα1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcα1→3GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcα1→3GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcβ1→4GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcβ1→4GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcβ1→4GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GalNAcβ1→4GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcβ1→4GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcβ1→4GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3GalNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galβ1→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galα1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galα1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Galα1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂--SO₂ --(CH₂)₇ --CH₃

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcα1→6Glcα1→4Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Glcα1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Glcβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇--CH₃

Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

NeuNAcα2→3GalO--CH₂ --CH CH₂ --S--CH₂)₁₅ --CH₃)₂

NeuNAcα2→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcα2→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

NeuNAcα2→3GalO-CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcα2→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcα2→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

NeuNAcα2→6GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

NeuNAcα2→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcα2→6GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

NeuNAcα2→6GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcα2→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcα2→6GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

NeuNAcα2→3GalNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

NeuNAcα2→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcα2→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

NeuNAcα2→3GalNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcα2→3GalNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcα2→3GalNAcO--CH₂ --C(═CH₂)--S--(CH₂)₁₀ --COOCH₃

NeuNAcα2→6GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

NeuNAcα2→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcα2→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

NeuNAcα2→6GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcα2→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcα2→6GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

NeuNAcα2→8NeuNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

NeuNAcα2→8NeuNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

NeuNAcα2→8NeuNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

NeuNAcα2→8NeuNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

NeuNAcα2→8NeuNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

NeuNAcα2→8NeuNAcO--CH.sub. --C(═CH₂)--S--(CH₂)₁₀ --COOCH₃

Glcβ1→4Glcβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcβ1→4Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcβ1→4Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Glcβ1→4Glcβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcβ1→4Glcβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcβ1→4Glcβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Glcα1→4Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcα1→4Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcα1→4Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Manα1→3(Manα1→6)ManO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Manα1→3(Manα1→6)ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Manα1→3(Manα1→6)ManO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Manα1→3(Manα1→6)ManO--CH₂ --CH(CH₂ --SO₂ CH₂ --CH₃)₂

Manα1→3(Manα1→6)ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Manα1→3(Manα1→6)ManO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀--COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --Ch₃

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3GalNAcβ1→4Galβ1-4GlcO--CH₂ C(═CH₂)--CH₂ S--(CH₂)₁₀ --COOCH₃

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅--CH₃)₂

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂--(CH₂)₁₅ --CH₃)₂

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂--(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂--CH₃)₂

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)₂ --COOCH₃

GalNAcβ1→4Galβ1→3GalNAcβ1→4Galβ1.fwdarw.4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)₁₀ --COOCH₃

GalNAcβ1→3Galα1→4galβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀--COOCH₃)--CH₂ SO₂ --(CH₂)₇ --CH₃

GalNAcβ1→3Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcβ1→3Galα1→4Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcβ1→3Galα1→4Galβ1→4GlcO--CH₂ --C(═CH₂ --S--(CH₂)₁₀ --COOCH₃

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀--COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GalNAcβ1→3Galα1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ S--(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀--COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→4GlcNAcβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅--CH₃)₂

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅--CH₃)₂

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀--COOCH₃)--CH₂ --SO₂ --(CH₂)₇ --CH₃

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂--CH₃)₂

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)₂ --COOCH₃

Galβ1→3GlcNAcβ1→3Galβ1→3Galβ1.fwdarw.4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)₁₀ --COOCH₃

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.3Galβ1→4GlcO--CH₂ --CH(CH₂--S--(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.Galβ1→4GlcO--CH₂ --CH(CH₂ SO₂--(CH₂)₁₅ --CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.3Galβ1→4GlcO--CH₂ --CH(CH₂--(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂ --(CH₂)₇ CH₃

Galβ1→4GlcNAcβ1→3GlcNAcβ1→3Galβ1.fwdarw.4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂--CH₃)₂

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)_(--COOCH) ₃

Galβ1→4GlcNAcβ1→3Galβ1→4GlcNAcβ1.fwdarw.3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂--S--(CH₂)₁₀ --COOCH₃ ##STR11## Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂--S--(CH₂)₁₅ --CH₃)₂

Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ CH₃

Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂--SO₂ --(CH₂)₇ --CH₃

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→3Galβ1→3Galβ1→4GlcO--CH₂ --C(═CH₂)--CH_(--S--)(CH₂)₁₀ --COOCH₃

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

GlcNAcβ1→3GalO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

GlcNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

GlcNAcβ1→3GalO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→4Glc(3Me)O--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→4Glc(3Me)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→4Glc(3Me)O--CH₂ --CH(CH₂ --SO₂ (CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galβ1→4Glc(3Me)O--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galβ1→4Glc(3Me)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galβ1→4Glc(3Me)O--CH₂ C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galα1→4Gal(3Me)O--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galα1→4Gal(3Me)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galα1→4Gal(3Me)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galα1→4Gal(3Me)O--CH₂ --CH(CH₂ --SO₂ --CH₂ CH₃)₂

Galα1→4Gal(3Me)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→4Gal(3Me)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galβ1→4Glc(3CH₂ OH)O--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galβ1→4Glc(3CH₂ OH)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galβ1→4Glc(3CH₂ OH)O--CH₂ --(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ CH₃

Galβ1→4Glc(3CH₂ OH)O--CH₂ --CH(CH₂ --SO₂ --CH₂ CH₃)₂

Galβ1→4Glc(3CH₂ OH)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ COOCH₃

Galβ1→4Glc(3CH₂ OH)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galα1→4Gal(3CH₂ OH)O--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galα1→4Gal(3CH₂ OH)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ CH₃)₂

Galα1→4Gal(3CH₂ OH)O--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galα1→4Gal(3CH₂ OH)O--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galα1→4Gal(3Ch₂ OH)O--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→4Gal(3CH₂ OH)O--CH₂ --C(═CH₂)₁₀ --COOCH₃

Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Galα1→4Galβ1→4GlcO--CH₂ --CH(CH₂ --SO₂ CH₂ CH₃)₂

Galα1→4Gal β1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→4Galβ1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Galα1→4Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --S--(CH₂)₁₅ --CH₃)₂

galα1→4Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Galα1→4Galβ1→4GlcNAcO-CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂--SO--(CH₂)₇ --CH₃

Galα1→4Galβ1→4GlcNAcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Galα1→4Galβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Galα1→4Galβ1→4GlcNAcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

Glcα1→6Glcα1→4GlcO--CH₂ --CH₂)--(CH₂ --S--(CH₂)₁₅ --CH₃)₂

Glcα1→6Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₅ --CH₃)₂

Glcα1→6Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --(CH₂)₁₀ --COOCH₃)--CH₂ --SO₂--(CH₂)₇ --CH₃

Glcα1→6Glcα1→4GlcO--CH₂ --CH(CH₂ --SO₂ --CH₂ --CH₃)₂

Glcα1→6Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₂ --COOCH₃

Glcα1→6Glcα1→4GlcO--CH₂ --C(═CH₂)--CH₂ --S--(CH₂)₁₀ --COOCH₃

In the compounds specified, the bond between the carbohydrate moiety inquestion and the aglycon moiety in question may be either in α- orβ-configuration.

In a different class of interesting compounds of the formula I, R₁ andR₃ are H and R₂ is --SO₂ --R₄ --R₅ wherein R₄ and R₅ are as definedabove. These compounds have a structure comprising a dimethylene groupconnecting the glycosidic oxygen and the sulphone group. As examples ofthe carbohydrate moiety in such compounds may be mentioned thecarbohydrate moieties listed above.

Compounds whose aglycon moiety terminates in an amino, hydroxy ormercapto group are also interesting. Such compounds include compounds inwhich R₃ is H, and R₁ and R₂ are groups of the formula II, of theformula III wherein R₆ is the group --R₄ -R₅, or the formula IIIawherein R₇ and/or R₇ is a group --R₄ -R₅, wherein R₄ is as definedabove, and R₅ is NH₂, OH or SH as well as compounds wherein R₂ and R₃together form ═CH₂, and R₁ is a group of the formula II, of the formulaIII, or of the formula IIIa with the same characteristics. Suchcompounds have the potential of being able to react with compounds ofthe formula I wherein R₃ is H, and R₁ and R₂ independently are a group--CH₂ X wherein X is a leaving group, or, in particular, compounds ofthe formula I in which R₂ and R₃ together form ═CH₂, and R₁ is a group--CH₂ X wherein X is a leaving group. Combination of compoundsincorporating a free amino, hydroxy or mercapto group with compoundsincorporating a leaving group X may result in the formation of bis- ortris-glycosides, thereby incorporating 2 or 3 carbohydrate moieties intothe same relatively small molecule. The carbohydrate units may beidentical, or they may be different thereby rendering possible theformation of compounds with multiple specificity.

The present invention also relates to a process for preparing anO-glycosidic compound of the formula I defined above.

A process (a) for preparing compounds in which R₃ is H, and R₁ and R₂are --CH₂ X, comprises reacting a sugar derivative of the formula V

    (Sugar).sub.n --Y                                          V

wherein Sugar and n are as defined above, and Y is acyl, halogen or agroup --S--R₉, wherein R₉ is lower alkyl or aryl or constitutes a linkbetween the anomeric oxygen and an oxygen or nitrogen atom in position 2of the saccharide unit (id est the latter is an ortho ester or oxazolinederivative), with an alcohol of the formula IX ##STR12## wherein X is asdefined above.

The reactions may be carried out in an aprotic, polar or non-polarorganic solvent such as methylene chloride, toluene, ether, ornitromethane. The reaction temperature is not critical, and the reactionmay be carried out at temperatures ranging from -78° C. to +150° C.,normally from 0° C. to 50° C. such as room temperature. The reactiontime may be from 0.1 to 200 hours, normally 1-24 hours such as 16 hours.A particularly useful example of the alcohol IX is a3-halo-2-halomethyl-propan-1-ol, in particular3-bromo-2-bromomethyl-propan-1-ol (DlBol). Such alcohols and derivativesthereof are described in Applicant's copending Danish applicationentitled "Propanol Derivatives", filed on the same date as the presentapplication. The alcohol of formula IX may be prepared by reduction withe.g. NaBH₄ of the corresponding acid where the acid is either known ormay be prepared by known methods. The preparation of DlBol isexemplified in Preparation 1 below. The alcohol of formula IX may beused in an excess of 1-2 molar equivalents based on the sugarderivative, in particular if Y is acyl such as acetyl. The reaction maybe carried out with the use of catalysts such as Lewis acids, e.g.BF₃.Et₂ O or SnCl₄, or metal salts such as silver oxide, silvercarbonate, silver triflate, HgBr₂, Hg(CN)₂. The metal salts areparticularly used if Y is halogen. Groups in the sugar derivative of theformula V that are sensitive to the reaction conditions may beprotected. Thus, the hydroxy groups may be protected with acyl groupssuch as acetyl or benzoyl, with benzyl, or with a benzylidene groupwherein the phenyl ring may be substituted with alkoxy in the4-position. When benzylidene groups are used as protection groups, twohydroxy groups are protected for each benzylidene group. The productformed may be purified by methods known in the art such as extraction,crystallisation or chromatography (preferably on silica gel). Theprotecting groups may, if desired, then be removed by methods known inthe art, optionally followed by further purification.

Another process (b) for preparing compounds in which R₃ is H, and R₁ andR₂ are of the formula II defined above comprises reacting an O-glycosideof the formula VI ##STR13## wherein Sugar, X and n are as defined abovewith a thiol of the formula VII

    H--R.sub.4 -R.sub.5                                        VII

wherein R₄ and R₅ are as defined above, and, if desired, reacting theproduct with an oxidizing agent.

The reaction may be carried out in water or in an aprotic or protic,polar or non-polar organic solvent such as ethyl acetate, methylenechloride, ether and dimethyl sulfoxide. The reaction temperature is notcritical, and the reaction may be carried out at temperatures between-30° C. and +150° C., normally from 0° C. to 50° C. such as roomtemperature. The reaction time may be from 0.1 to 200 hours, normallyfrom 10 to 72 hours such as 24-48 hours. The reaction is generallycarried out with slightly more than 2 equivalents of the thiol of theformula VII per equivalent of the O-glycoside of formula VI. It isgenerally necessary to add a base to the reaction mixture, although thebase should not be too strong. Examples of useful bases are cesiumcarbonate, potassium carbonate, sodium carbonate, sodium hydroxide,potassium hydroxide, as well as pyridine and substituted pyridines. Thebase should preferably be added after the thiol in order to avoidelimination reactions in the O-glycoside of the formula VI. Protectinggroups in the carbohydrate moiety of the O-glycoside of the formula VImay be the ones described in connection with process (a) above. Theproduct compound may be purified and deprotected by the methodsdescribed in connection with process (a). The glycoside startingmaterial of formula VI may be prepared as described in process (a).

The oxidation of the resulting thio compounds may occur in two steps,viz. on the one hand through attachment of one oxygen atom on eachsulphur atom resulting in the sulphoxides, or through attachment of twooxygen atoms to each atom resulting in the corresponding sulphones. Inorder to oxidize only to the sulphoxide compounds, two equivalents ofoxidizing agents are used. For oxidation to the sulphones, fourequivalents or more of oxidizing agent are used. Examples of usefuloxidizing agents are peracids, e.g. m-chloroperbenzoic acid; peroxides,e.g. tert.butyl hydroperoxide; aminooxides, gaseous oxygen, or inorganicoxidizing agents such as potassium permanganate, chromium trioxide, etc.The oxidation reaction may be carried out in the same medium as thepreceding thio-ether-forming reaction and without purifying ordeprotecting the bis-thio compound. The reaction is carried out at atemperature between -78° C. and +100° C., normally from 0° C. to 50° C.such as room temperature.

A process (c) for preparing compounds in which R₂ and R₃ together form=CH₂, and R₁ is CH₂ X comprises reacting an O-glycoside of the formulaVI defined above with a base. The reaction may be carried out in wateror in an protic or protic, polar or non-polar organic solvent such asethylacetate, methylene chloride, ether or dimethylsulphoxide. Thereactions may be carried out at temperatures between -30° C. and +150°C., normally from 0° C. 50° C. such as room temperature for a period of0.1-200 hours, normally 8-24 hours such as 16 hours. The carbohydratemoiety of the O-glycoside of the formula VI may be equipped withprotecting groups of the type described in process (a). The base may beof the same type as described in process (b), but may, however, also bea stronger base such as sodium hydride or butyllithium. The productformed (having the formula VIII below) may be purified and deprotectedby the methods described in the preceding processes.

In a further process (d), compounds are prepared in which R₂ and R₃together form ═CH₂, and R₁ is a group of the formula II defined above.The process comprises reacting an O-glycoside of the formula VIII##STR14## with a thiol of the formula VII defined above, and, ifdesired, reacting the product with an oxidizing agent. The reaction withthe thiol may be carried out under the same conditions as thosedescribed for the corresponding thio-ether-forming step in process (b),although in the present process the base may be added before the thiol.The oxidation reaction may be carried out using the same oxidationagents described in process (b) and under the same conditions, with theexception that for the preparation of the sulphoxide, only oneequivalent of oxidizing agent is used, and for the preparation ofsulphones, two or more equivalents of oxidizing agents are used. Theproducts may be purified as described in the previous processes. Theglycoside starting material of formula VIII may be prepared as describedin process (c) above.

In a further process (e), compounds are prepared in which R₂ and R₃together form ═CH₂ and R₁ is a group of the formula III defined above.The process comprises reacting an O-glycoside of the formula VIIIdefined above with an alcohol R₆ --OH wherein R₆ is as defined above.The reaction may be carried out under conditions similar to thosedescribed for the thio-ether-forming step in process (b) above.

In a further process (f), compounds are prepared in which R₂ and R₃together form ═CH₂ and R₁ is of the formula IIIa defined above. Theprocess comprises reacting an O-glycoside of the formula VIII definedabove with an amine R₇ R'₇ NH, wherein R₇ and R'₇ are as defined above.The reaction conditions may be similar to those described in thethio-ether-forming step in process (b) above.

A process (g) for preparing the polymers of the formula XX iscontemplated. The process comprises reacting an O-glycoside of theformula VI defined above with a dithiol HS--R₄ --SH wherein R₄ is asdefined above. The reaction conditions are similar to those described inthe thio-ether-forming step in process (b).

Another process (h) for preparation of the polymers of the formula XXIis also contemplated. The process comprises reacting an O-glycoside ofthe formula VI defined above with a trithiol of the formula ##STR15##wherein R₄ is as defined above. As in process (g), the reactionconditions may be similar to those described in the thio-ether-formingstep in process (b) above.

In yet another process (i), compounds of the formula I may be preparedby reacting a compound of the formula Ia ##STR16## wherein Sugar, R₁, R₂and R₃ are as defined above, and r is an integer from 1 to 9 inclusive,with a sugar derivative of the formula Va

    (Sugar).sub.n-r --Y                                        Va

wherein Sugar, Y, n and r are as defined above. The Sugar moiety of thecompound of formula Ia is preferably suitably protected, and it isparticularly preferred that there is only one unprotected hydroxy group.The reaction may be carried out on conditions similar to those describedin process (a) using Lewis acid or metal salt catalysts. By thisprocess, the Sugar moiety of an already prepared O-glycoside of formulaI may be modified or converted to obtain a different O-glycoside of theformula I.

In yet another process (j), compounds of the formula I in which R₃ is Hand R₁ and R₂ are not --CH₂ X may be prepared by reacting a compound ofthe formula V as defined above with an alcohol of the formula X##STR17## wherein R' and R" which may be the same or different have thesame meaning as R₁ and R₂ above except that R' and R" are not --CH₂ X.The reaction conditions may be similar to those described in process (a)above.

The compounds of formula I may be used as synthetic receptors for a widevariety of biological entities. The receptor-specific unit of naturalreceptors is generally a carbohydrate unit although parts of the"spacer-arm" carrying the carbohydrate unit may also form part of thereceptor by providing a specific environment and/or overall spatialshape to the receptor unit. In general, in the compounds of the formulaI, the carbohydrate moiety is selected according to what type of agent(e.g. microorganism, virus, blood protein, antibody, etc.) for which areceptor is desired. The aglycon moiety of the compound of the formula Iwill generally determine the physical manner in which the receptor isused. Thus, the aglycon moiety may be a lipid function (with either oneor two lipophilic "tails") making it possible to incorporate thecompounds into a biological membrane or through a micelle. As a resultof the structure of the part of the aglycon moiety close to thecarbohydrate unit, the compounds of the formula I are able to mimicnatural receptors. This similarity in structure will be evident whencomparing the structure of the synthetic glycolipids shown below withthe structure of the natural glycolipids shown previously.

A further advantage with the compounds of formula I, wherein R₃ ═H, R₁=--CH₂ --S(O)_(m) (O)_(p) --R₄ R₅ with R₄ =alkyl chain and R₅ ═COOH andR₂ =--CH₂ --S(O)_(m) (O)_(p) --R₄ R₅ with R₄ =alkyl chain and R₅ ═CH₃ orCOOH, is that these compounds are water soluble while at the same timethey are "mimics" of natural glycolipids. This is a new physicalproperty of compounds that perform in a way that is similar to naturalglycolipids with regard to receptor activity towards e.g. viruses (seebelow).

Allyl-thio compounds have the advantage of being easily hydrogenated(c.f. A. S. Birch and K. A. M. Walker, Tetrahedron Lett. (1967) p.(1935). This can be applied to the allyl-thio glycosides of the presentinvention for radioactive labelling with catalytic tritiation.

    __________________________________________________________________________                                                      SYNTHETIC                                                                     GLYCOPLIPIDS                __________________________________________________________________________     ##STR18##                                        BIS-THIOGLYCOLIPID           ##STR19##                                        BIS-SULFOXIDE GLYCOLIPID                                                      1                            ##STR20##                                        BIS-SULFONE GLYCOLIPID       ##STR21##                                        ALLYL-THIO GLYCOLIPID       __________________________________________________________________________

Through the use of sulfoxide or sulfone groups in the molecule, it ispossible to "fine-tune" the hydrophilic/hydrophobic and polar/apolarproperties of the aglycon moiety which may be of importance e.g. whenattempts are made to mimic natural receptors in which part of theaglycon moiety also defines the receptor such as in the secondarypenetration-receptor in certain vira.

The aglycon moiety may also be a "spacer-arm" attached to a carrier ofthe types suggested above; or the aglycon part may be a unit with areactive terminal making it possible to incorporate any specificreceptor into e.g. a carrier structure of some kind. The activation ofthe reactive terminal could conceivably be carried out before as well asafter the receptor has attached itself to the agent, to which it hasbeen designed. A central feature of the present invention is thepossibility of easily incorporating receptors specific for a widevariety of biological agents into a desired structure. The possibilitiesopened through the invention are multifarious. The compounds of theformula I may form part of or be incorporated in products likepharmaceutical compositions for therapeutic or prophylactic treatment ofbacterial or viral diseases (e.g. injectables comprising micelles,liposomes or microscopic beads, implants, tablets, lozenges, or chewingtablets for oral prophylactic use, etc.); diagnostic tools such as inRIA- and ELISA-methods, diagnostic dip-sticks, agglutination kits,immunological test cards or blood test cards (through incorporation ofthe compounds of formula I on appropriate carrier materials such asplastics); disinfection means such as fluids (for cleaning e.g. surgicalwounds) or paper tissues incorporating specific receptors towardscertain biological agents (e.g. vira such as common cold, herpes, andother vira, bacteria transmitting various infectious diseases, etc.).

With respect to treatment or prophylaxis against viral or bacterialinfectious diseases, one important use aspect is in connection withepithelial cells and at the port-of-entry of various infections.Examples of such port-of-entries are the mucos membranes of the eye,nose, oral cavity, throat, respiratory tract, gastro-intestinal tract,urinary tract and reproductive organs. Treatment or prophylaxis may beobtained by direct application on the mucous membranes of the compoundsof the formula I in a pharmaceutically acceptable form such as asuspension, an aerosole, an ointment or a solution. On the mucousmembranes, the active compounds will bind to bacteria or, in particular,vira thereby reducing the infecting ability of the organisms inquestion.

The compounds of the formula I may, however, also be used as systemicagents for intravenous, intramuscular, intraperitoneal or subcutaneousinjection. The composition for this use may be in the form of asolution, an emulsion or a suspension of either compounds in a solidform or the compounds incorporated on various of the carriers describedabove. The compounds of the formula I may furthermore be administered inthe form of nasal or oral sprays.

Other uses of the compounds of the formula I include flushing of theurinary tract, intestines, etc.

Another interesting use of the compounds of the formula I is asvaccines. If the carbohydrate moiety is of a type occurring in bacteriaand/or vira, such compounds of the formula I may act as antigenespromoting the formation of antibodies in the host animal, e.g. a human.The ability to promote the formation of antibodies may, however, also beexploited in vitro for the production of monoclonal antibodies in cellcultures.

Since the receptor-specific binding between spermatozoa and ova is alsobased on carbohydrates, the compounds of the formula I may conceivablyalso be used as a contraceptive agent incorporated in e.g. anintravaginal device such as a sponge or a tampon.

In view of the above, the present invention also relates topharmaceutical or diagnostic compositions comprising one or morecompounds of the formula I, optionally in combination with apharmaceutically acceptable excipient.

The pharmaceutical composition may be in the form of tablets, capsules,lozenges, sirups, injectable solutions, injectable emulsions, implants,or suppositories. The excipient may be any of the excipients commonlyused within the art. For solid compositions may be used conventionalnon-toxic solid excipients including e.g. pharmaceutical grades ofmannitol, lactose, starch, magnesium stearate, sodium saccharin, talc,cellulose, saccharose, magnesium carbonate or the like. Liquidpharmaceutically administrable compositions may e.g. be prepared bydissolving, dispersing etc. the active compound and an optionalpharmaceutical adjuvant in an excipient such as water, salt water,aqueous dextrose, glycerol, ethanol, etc. in order to form a solution orsuspension. If desired, the pharmaceutical composition to beadministered may also contain minor amounts of non-toxic additives suchas wetting or emulsifying agents, pH-buffers etc., e.g. sodium acetate,sorbitan monolaurate, triethanol amine, etc. The active compound mayalso be formulated as suppositories, using e.g. polyalkylene glycolssuch as propylene glycol as an excipient. The actual preparation of suchdosage forms are well known or will be evident to persons skilled in theart, cf. e.g. Remingtons Pharmaceutical Sciences, Mack PublishingCompany, Easton, Pa., 15th Edition, 1975.

For intravenous injections, the compound (optionally bound to a carrier)is dissolved in an aqueous medium buffered to the desired pH and treatedin order to control isotonicity.

Since the compounds of the formula I are useful in connection with themucos membranes, the compounds may also be administered in the form ofan aerosol.

When administered as an aerosol, the active compound is preferably givenin a finely divided form together with a surfactant and a propellant.

The dosages in which the compounds of the formula I are administered mayvary widely depending on the intended use, whether for prophylaxis,including disinfection, or therapy, the type of infection to becombated, the age and condition of the patient, etc., but is expected tobe at a milligram level. For rotavirus infection (diarrhoea), a dailydose of 1 μg receptor per human individual has been calculated toagglutinate/inactivate all viruses produced during one day, provided thereceptor is bivalent and only one bivalent receptor is used per virusparticle. In practice, of course, a far larger dosage is needed tosecure an effective binding of all the virus particles present. Contraryto what is the case with most medicaments now in use, the dosage levelmay not be so essential since the toxic effects of the compounds offormula I are expected to be negligible since, in fact, at least thenatural receptors are substances which are present in large amounts inthe human or animal system.

Cerain compounds of the formula I such as bis-sulfide glycolipids, i.e.compounds of the formula I in which R₃ is H, and R₁ and R₂ are groups ofthe formula II wherein m and p both are 0, R₄ is an alkyl chain, and R₅is H, have been found to exhibit remarkable properties in that they areable to form liquid crystals in aprotic media such as dimethylsulphoxide (cf. Example 7). It is contemplated that other similarsubgroups of compounds of the formula I have the same properties. To thebest of Applicant's knowledge, this is the first time that liquidcrystals have been prepared in an aprotic medium, and this particularproperty may render possible the formation of liquid crystals withhigher stability in electrical fields. Such liquid crystals mayconceivably be used in e.g. visual displays with lifetimes superior tothose possible at the present time.

The invention is further illustrated by the following non-limitingpreparation and examples. Preparation 1 describes the preparation of thestarting material DlBol, which has been subject to a separate patentapplication, submitted at the same data as the present application.

PREPARATION 1 3-Bromo-2-bromomethylpropan-1-ol (DlBol)

3-Bromo-2-bromomethylpropanoic acid (15.3 g; 62 mmol) (cf. A. F. Ferris,J. Org. Chem., 20 (1955) p 780) was dissolved in dry dichloromethane(400 ml) and cooled (0°). The reaction mixture was kept under nitrogen.A solution of diborane in tetrahydrofuran (190 ml; 190 mmol; 1M solutionof BH₃ in THF) was added dropwise with stirring. After 1 hour, thecooling bath was removed and the mixture was left overnight at roomtemperature. Hydrochloric acid (210 ml; 1M) was added, the organic phasewas separated and the aqueous phase was extracted with dichloromethane(3×50 ml). The combined organic phases were dried (Na₂ SO₄) andconcentrated. Flash chromatography of the residue gave pure DlBol (13.8g; 96%). Bp ca. 45° C. (0.1 mm Hg); n_(D) ²³ 1.5439;

IR-spectrum: ν_(max). =3340 cm¹

¹ H-NMR (CDCl₃, Me₄ Si) δ(ppm)=3.79 (d, 2 H, J=6.0 Hz, CH₂ --O), 3.59(d, 4 H, J=5.7 Hz, CH₂ Br), 2.27 (heptet, 1 H, J=6 Hz, CH(CH₂)₃ ;

¹³ C-NMR (CDCl₃, Me₄ Si): δ(ppm)=62.4 (CH₂ OH), 44.4 (CH), 32.8 (CH₂Br);

Analysis calculated for C₄ H₈ Br₂ O C 20.7, H 3.48 Found: C 21.0, H 3.73

EXAMPLE 1 Preparation of DIB glycosides

(a) Borontrifluoride etherate (0.7 ml) was added dropwise with stirringto a solution of a fully acetylated sugar (1 mmol) and DlBol (232 mg; 1mmol) in dichloromethane (3 ml) at room temperature. After 2-4 h, themixture was washed with water and sodium hydrogencarbonate solution,dried (Na₂ SO₄), and concentrated. The residue was subjected tochromatography (SiO₂, ethyl acetate: hexane) to give the DIB glycosidein pure form (see Table 1). The following compounds were prepared:3-Bromo-2-bromomethylprop-1-yl2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (DIB-1). From1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose. Yield: 54%. [α]_(D) ²³ =-5°(c=0.6 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ(ppm)=5.22 (t, 1H, J₂,3 =J₃,4 =9.7 Hz, H-3),5.1 (t, 1H, J₄,5 =9.4 Hz, H-4), 4.99 (t, 1H, H-2), 4.51 (d, 1H, J₁,2=7.9 Hz, H-1), 4.27, 4.15 (ABq with further coupling, each 1H, J_(AB)=12.6 Hz, J₅,6 =4.0 Hz, H-6,6'), 3.71 (m, 1H, H-5), 2.34 (m, 1 H,CH(CH₂)₃).

Analysis: Calculated for C₁₈ H₂₆ Br₂ O₁₀ : C 38.5, H 4.66 Found: C 38.4,H 4.69

3-Bromo-2-bromomethylprop-1-yl2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (DIB-2). From1,2,3,4,6-penta-O-acetyl-β-D-galactopyranose. Yield: 50%. [α]_(D) ²³=+1° (c=0.7 in CDCl₃). NMR-Spectrum (CDCl₃, TMS): δ(ppm)=5.40 (d, 1H,j₃,4 =3.2 Hz, H-4), 5.19 (dd, 1H, J₂,3 =10.4 Hz, H-2), 5.03 (dd, 1H,H-3), 4.47 (d, 1H, J₁,2 =7.6 Hz, H-1), 4.19, 4.13 (ABq with furthercoupling, each 1H, J_(AB) =11.2 Hz, J₅,6 =J₅,6 =6.5 Hz, H-6.6'), 3.92(t, 1H, J₄,5 =0.4 Hz, H-5), 2.35 (septet, 1H, J=5.8 Hz, CH(CH₂)₃).

Methyl (3-bromo-2-bromomethylprop-1-yl2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronate (DIB-3). From methyl(1,2,3,4-tetra-O-acetyl-β-D-glucopyranose)uronate. Yield: 26%. [α]_(D)²³ =+3° (c=1.1 in CDCl₃). NMR-Spectrum (CDCl₃, TMS): δ(ppm)=5.33-5.16(m, 2H, H-3,4), 5.01 (m, 1H, H-2), 4.55 (d, 1H, J₁,2 =7.6 Hz, H-1), 4.04(d, 1H, J₄,5 =9.4 Hz, H-5), 3.77 (s, 3H, OCH₃), 2.34 (septet, 1H, J=6.1Hz, CH(CH₂)₃).

3-Bromo-2-bromomethylprop-1-yl-3,4,6-tri-O-acetyl-2deoxy-2-phthalimido-.beta.-D-glucopyranoside(DIB-4). From1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-α/β-D-glucopyranose (α/βratio 1/1). Yield: 52%. [α]_(D) ²³ =20° (c=1.0 in CDCl₃). NMR-Spectrum(CDCl₃, TMS): δ(ppm)=5.82 (t, 1H, J₃,4 =10.1 Hz, H-3), 5.36 (d, 1H, J₁,2=8.3 Hz, H-1), 5.17 (t, 1H, J₄,5 =10,1 Hz, H-4), 4.32 (dd, 1H, J₂,3=10.4 Hz, H-2), 4.33, 4.19 (ABq with further coupling, each 1H, J_(AB)=12.2 Hz, J₅,6 =5.0 Hz, J₅,6 =2.2 Hz, H-6,6'), 3.89 (m, 1H, H-5), 2.24(m, 1H, J=5.8 Hz, CH(CH₂)₃).

3-Bromo-2-bromomethylprop-1yl 2,3,4-tri-O-acetyl-β-D-xylopyranoside(DIB-5). From 1,2,3,4-tetra-O-acetyl-α/β-D-xylopyranose (α/β ratio 1/1).Yield: 50% [α]_(D) ²³ =-25° (c=0.9 in CDCl₃). NMR-Spectrum (CDCl₃, TMS):δ(ppm)=5.18 (t, 1H, J₂,3 =J₃,4 =8.3 Hz, H-3), 4.98-4.89 (m, 2H, H-2,4),4.49 (d, 1H, J₁,2 =6.7 Hz, H-1), 4.14, 3.39 (ABq with further coupling,J_(AB) =11.5 Hz, J₄,5 =5.0 Hz. J₄,5' =9.0 Hz, H-5,5'), 2.34 (septet,J=5.6 Hz, CH(CH₂)₃).

3-Bromo-2-bromomethylprop-1-yl2,3,6-tri-O-acetyl-4,0-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(DIB-6). From1,2,3,6-tetra-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranose.Yield: 60%: [α]_(D) ²³ =-6° (c=0.7 in CDCl₃). NMR-Spectrum (CDCl₃, TMS):δ(ppm)=5.35 (d, 1H, J_(3'),4' =2.9 Hz, H-4'), 5.20 (t, 1H, J₂,3 =9.0 Hz,H-2), 5.11 (dd, 1H, J_(1'),2' =7.9 Hz, J_(2'),3' =10.1 Hz, H-2'), 4.95(dd, 1H, H-3'), 4.89 (t, 1H, J₃,4 =9.0 Hz, H-3), 4.50, 4.47 (two d, each1H, J=7.9 Hz, H-1,1'), 2.23 (septet, 1H, J=5.8 Hz, CH(CH₂)₃).

Analysis: Calculated for: C₃₀ H₄₂ Br₂ O₁₈ : C 42.4 H 4.98 Found: C 42.4H 4.92

3-Bromo-2-bromomethylprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(DIB-7). From1,2,3,6-tetra-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-α-D-galactopyranose.Yield: 43%. [α]_(D) ²³ =+68.6° (c=1.5 in CDCl₃). NMR-Spectrum (CDCl₃,TMS): δ(ppm)=5.58 (dd, 1H, J_(4'),5' =1.0 Hz, H-4'), 5.39 (dd, 1H,J_(2'),3' =10.8 Hz, H-2'), 5.20 (dd, 1H, J_(3'),4' =3.6 Hz, H-3'), 5.17(dd, 1H, J₂,3 =10.8 Hz, H-2), 5.01 (d, 1H, J_(1'),2 =3.2 Hz, H-1'), 4.82(dd, 1H, J₂,4 =2.9 hz, H-3), 4.47 (d, 1H, J₁,2 =7.6 Hz, H-1), 2.37(septet, 1H, J=5.8 Hz, CH(CH₂)₃).

(b) Acetobromolactose (3.15 g; 4.51 mmol) and silvertrifluoromethansulfonate (1.93 g; 7.5 mmol) were dried in atwo-compartment reaction vessel as described by Nashed & Andersson(1982). DlBol (1.25 g; 5.39 mmol) in dichloromethane (10 ml) andtetramethylurea (1.3 g; 11.3 mmol) in dichloromethane (10 ml) were addedand the reaction mixture was stirred overnight. The reaction vessel wasprotected from light by means of aluminum foil. When theacetobromolactose had been consumed, the reaction mixture was filteredthrough Celite, concentrated and chromatographed to give the DIBβ-lactoside (DIB-6, 2.7 g; 73%); see above and Table 1.

Using the same procedure as above but with2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-α-D-galacto-pyranosylbromide (2.65 g, 3.80 mmol) (cf. Dahmen et al. Carbohydr. Res., 116(1983)) and acetylation of the crude reaction mixture, permitted theisolation of DIB-7 (1.88 g, 39%) and the corresponding α-glycoside (0.24g, 7%).

(c) DIB 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (562 mg; 1 mmol) maybe deacetylated as described in Example 2 to give DIBβ-D-glucopyranoside which is transformed into DIB4,6-benzylidene-β-D-glucopyranoside by treatment with dimethoxytolueneunder acidic conditions. Treatment with benzyl chloride and sodiumhydride in dimethylformamide gives DIB2,3-di-O-benzyl-4,6-benzylidene-β-D-glucopyranoside which in turn isreduced with sodium cyanoborohydride in ether (cf. Nashed & Andersson(1982) to give 2,3,6-tri-O-benzyl-β-D-gluco pyranoside. Reaction withacetobromogalactose and silver trifluoromethane sulfonate (AgTf),essentially as under (b) above, gives the expected DIB lactoside, whichis hydrogenated to cleave off the benzyl groups. Acetylation in thenormal way, followed by chromatography, gives the pure DIB lactoside(DIB-6) as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR22##                                                                    Com-                                                                          pound                                                                         no.    R'.sub.1                                                                              R'.sub.2                                                                             R'.sub.3                                                                           R'.sub.4                                                                             R'.sub.5                                                                             R'.sub.6                             ______________________________________                                        DIB-1  DAc.sup.a                                                                             H      OAc  OAc    H      CH.sub.2 OAc                         DIB-2  OAc     H      OAc  H      OAc    CH.sub.2 OAc                         DIB-3  OAc     H      OAc  OAc    H      COOCH.sub.3                          DIB-4  NPhth.sup.b                                                                           H      OAc  OAc    H      CH.sub.2 OAc                         DIB-5  OAc     H      OAc  OAc    H      H                                    DIB-6  OAc     H      OAc  GalAcβ.sup.c                                                                    H      CH.sub.2 OAc                         DIB-7  OAc     H      OAc  H      GalAcα.sup.d                                                                   CH.sub.2 OAc                         ______________________________________                                         .sup.a Ac = acetyl;                                                           .sup.b Phth = phthaloyl;                                                      .sup.c GalAcβ = 2,3,4,6-tetra-Oacetyl-β-Dgalactopyranosyl;          .sup.d GalAcα = 2,3,4,6-tetra-Oacetyl-α-Dgalactopyranosyl.   

EXAMPLE 2 Preparation of bis-sulfide glycosides

A fully acetylated DIB glycoside (0.38 mmol), an alkyl thiol (1 mmol),cesium carbonate (338 mg; 1 mmol) and dimethylformamide (2 ml) werestirred at room temperature under nitrogen for 24-48 hours. The reactionwas monitored by TLC (SiO₂, ethyl acetate: hexane). Dichloromethane (40ml) was added and the mixture was washed with water (2×5 ml), dried (Na₂SO₄) and concentrated. Column chromatography (SiO₂, ethyl acetate:hexane) gave the pure, fully acetylated glycoside (see Table 2).

The acetylated glycoside (0.2 mmol) was dissolved in dichloromethane (15ml) and methanolic sodium methoxide (10 ml; prepared by dissolving ca. 1mg of sodium in methanol) was added. The reaction was monitored by TLC(chloroform:methanol:water, 65:35:10). In some cases, a precipitate wasformed towards the end of the reaction. One drop of acetic acid wasadded and the reaction mixture was concentrated, suspended in water (10ml) and freeze-dried to give a qunatitative yield of the unprotectedglycolipid, contaminated with small amounts of sodium acetate (ca. 1%w/w). The following compounds were prepared:

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,4,6-tetra-O-acetyl-β-D-glycopyranoside (RSC16-1). From DIB-1 andhexadecanethiol. Yield: 70%. [α]_(D) ²³ =-1.6° (c=1.1 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.20 (t, 1H, J₂,3 =9.3 Hz, H-3), 5.06(t, 1H, J₃,4 =J₄,5 =9.5 Hz, H-4), 4.98 (dd, 1H, H-2), 4.48 (d, 1 H, J₁,2=7.9 Hz, H-1), 4.26, 4.11 (ABq with further coupling, each 1 H, J_(AB)=12.4 Hz, J₅,6 =4.8 Hz, J₅,6' =2.5 Hz, H-6,6'), 2.6-2.4 (m, 8 H, CH₂-S).

Analysis: Calculated for C₅₀ H₉₂ O₁₀ S₂ : C 65.5 H 10.1 Found: C 65.7 H10.2

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (RSC16-2). From DIB-2 andhexadecanethiol. Yield: 79%. [α]_(D) ²³ =+1° (c=1.6 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.37 (dd, 1 H, J₄,5 =0.8 Hz, H-4),5.17 (dd, 1 H, J₂,3 =10.3 Hz, H-2), 4.99 (dd, 1 H, J₃,4 =3.4 Hz, H-3),4.44 (d, 1H, J₁,2 =7.8 Hz, H-1), 2.7-2.4 (m, 8 H, CH₂ -S).

Analysis: Calculated for C₅₀ H₉₂ O₁₀ S₂ : C 65.5 H 10.1 Found: C 65.3 H10.2

Methyl (3-hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,4-tri-O-acetyl-β-D-glucopyranosyl)-uronate (RSC16-3). From DIB-3 andhexadecanethiol. Yield: 68%. [α]_(D) ²³ =1.7° (c=0.9 in CDCl₃.NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.25 (t, 1 H, J₃,4 =9.0 Hz, H-3),5.20 (t, 1 H, J₄,5 =9.4 Hz, H-4), 5.01 (dd, 1 H, J₂,3 =9.0 Hz, H-2),4.54 (d, 1 H, J₁,2 =7.6 Hz, H-1), 4.03 (d, 1 H, H-5), 3.76 (s, 3 H,O-CH₃), 2.60-2.45 (m, 8 H, CH₂ -S).

Analysis: Calculated for C₄₉ H₉₀ O₁₀ S₂ : C 64.7 H 10.2 Found: C 64.9 H10.2

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside (RSC16-4).From DIB-4 and hexadecanethiol. Yield: 81%. [α]_(D) ²³ =+11.6° (c=1.1 inCDCl₃). NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.80 (dd, J₂,3 =10.7 Hz,H-3), 5.32 (d, 1 H, J₁,2 =8.5 Hz, H-1), 5.16 (t, 1 H, J₃,4 =J₄,5 =9.2Hz, H-4), 2.5-2.2 (m, 8 H, CH₂ -S).

Analysis: Calculated for C₅₅ H₉₃ NO₁₀ S₂ : C 67.0 H 9.33 N 1.39 Found: C67.0 H 9.52 N 1.39

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,4-tri-O-acetyl-β-D-xylopyranoside (RSC16-5). From DIB-5 andhexadecanethiol. Yield: 61%. [α]_(D) ²³ =-17.6° (c=1.1 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.15 (t, 1 H, J₂,3 =J₃,4 =8.5 Hz,H-3), 4.98-4.85 (m, 2 H, H-2,4), 4.45 (d, 1 H, J₁,2 =6.7 Hz, H-1), 4.10,3.34 (ABq with further coupling, each 1 H, J_(AB) =12.0 Hz, J₄₅ =5.0 Hz,J₄,5' =8.8 Hz, H-5,5'), 2.7-2.4 (m, 8 H, CH₂ -S).

Analysis: Calculated for C₄₇ H₈₈ OHD 8S₂ : C 66.8 H 10.5 Found: C 66.7 H10.6

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSC16-6). From DIB-6 and hexadecanethiol. Yield 88%. [α]_(D) ²³ =-4.1°(c=0.8 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.34 (d, 1 H, H-4'), 5.19 (t, 1 H,J₂,3 =9.0 Hz, H-2), 5.10 (dd, 1H, J_(2'),3' =10.4 Hz, H-2'), 4.95 (dd,1H, J_(3'),4' =3.6 Hz, H-3'), 4.89 (dd, 1 H, J₃,4 =7.9 Hz, H-3), 4.474.46 (two d, each 1 H, J=7.6 Hz and 7.9 Hz, H-1,1'), 2.6-2.45 (m, 8 H,S-CH₂).

Analysis: Calculated for C₂₆ H₁₀₈ O₁₈ S₂ : C 61.8 H 9.03 Found: C 62.0 H9.32

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(RSC16-7). From DIB-7 and hexadecanethiol. Yield: 51%. [α]_(D) ²³ =+52°(c=0.6 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.57 (dd, 1 H, J_(4'),5' =0.8 Hz,H-4'), 5.38 (dd, 1 H, J_(2'),3' =11.0 Hz, H-2'), 5.18 (dd, 1 H,J_(3'),4' =3.7 Hz, H-3'), 5.16 (dd, 1 H, J₂,3 =11.0 Hz, H-2), 4.99 (d,1H, J_(1'),2' =3.3 Hz, H-1'), 4.79 (dd, 1 H, J₃,4 =2.8 Hz, H-3), 4.44(d, 1 H, J₁,2 =7.7 Hz, H-1), 2.7-2.45 (m, 8 H, S-CH₂).

Analysis: Calculated for C₆₂ H₁₀₈ O₁₈ S₂ : C 61.8 H 9.03 Found C 60.7 H9.00

3-Octadecylthio-2-octadecylthiomethylprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSC18-1). From DIB-6 and octadecanethiol. Yield: 67%. [α]_(D) ²³ =-3.4°(c=0.8 in CDCl₃). NMR-Spectrum (CDCl₃, TMS): practically identical withthe spectra of RSC16-6 and RSC8-1.

3-Octylthio-2-octylthiomethylprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,-6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSC8-1). From DIB-6 and octanethiol. Yield: 73%. [α]_(D) ²³ =-4.9°(c=0.8 in CDCl₃). NMR-Spectrum (CDCl₃, TMS): practically identical withthe spectra of RSC16-6 and RSC18-1.

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl β-D-glucopyranoside(RSC16-8). From RSC16-1. [α]_(D) ²³ =-7° (c=0.9 in CMD(CDCl₃ /-CD₃ OD/D₂O, 65:35:10). NMR-Spectrum (CMD, TMS, 50°): δ (ppm)=4.29 (d, 1 H, J₁,2=7.6 Hz, H-1), 2.70 (d, 4 H, J=6.4 Hz, CH--(CH₂ --S)₂), 2.53 (t, 4 H,J=7.3 Hz, S--CH₂ --CH₂).

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl β-D-galactopyranoside(RSC16-9). From RSC16-2. [α]_(D) ²³ =-3° (c=0.5 in CMD). NMR-Sepctrum(CMD, TMS, 20°): δ (ppm)=4.24 (virtual coupling, J₁,2 =7.6 Hz, H-1),2.71 (d, 4 H, J=6.7 Hz, CH--(CH₂ --S)₂), 2.53 (t, 4H, J=7.2 Hz, S--CH₂--CH₂).

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl β-D-xylopyranoside(RSC16-12). From RSC16-5. [α]_(D) ²³ =-6° (c=0.5 in CMD). NMR-Spectrum(CMD, TMS, 50°): δ (ppm)=4.25 (d, 1 H, J=7.1 Hz, H-1), 2.69 (d, 4 H,J=6.4 Hz, CH--(CH₂ --S)₂), 2.53 (t, 4 H, J=7.5 Hz, S--CH₂ --CH₂).

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSC16-13). From RSC16-6.[α]_(D) ²³ =-3.5° (c=1.6 in CMD). NMR-Spectrum (CMD, TMS, 40°): δ(ppm)=4.31 (d, 2 H, J=7.8 Hz, H-1,1'), 2.71 (d, 4 H, J=6.6 Hz, CH--CH₂--5), 2.53 (t, 4 H, J=7.3 Hz, S--CH₂ --CH₂).

3-Hexadecylthio-2-hexadecylthiomethylprop-1-yl4-O-α-D-galactopyranosyl-β-D-galactopyranoside (RSC16-14). From RSC16-7.[α]_(D) ²³ =+28° (c=0.6 in CMD). NMR-Spectrum (CMD, TMS, 50°): δ(ppm)=5.01 (d, 1 H, J_(1'),2' =2.5 Hz, H-1'), 4.27 (d, 1 H, J₁,2 =7.2Hz, H-1), 2.72 (d, 4 H, J=6.3 Hz, CH--(CH₂ --S)₂), 2.53 (t, 4 H, J=7.4Hz, S--CH₂ --CH₂).

3-(10-Methoxycarbonyldecylthio)-2-(octylthiomethyl)-prop-1-yl2,3,6-tri-O-acetyl-4-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSC10EC8).

DIB-6 (291 mg, 0.34 mmol was dissolved in dry dimethylformamid (1 ml).Octylthiol (50 mg, 0.34 mmol) in dimethylformamid (1 ml) was added,followed by cesium carbonate (112 mg), 0.34 mmol). After stirring for 70h at 20°, water (15 ml) was added and the mixture was extracted withdichloromethane (2×10 ml). The extract was dried (Na₂ SO₄) andconcentrated by several additions of toluene to remove remainingdimethylformamide. The residue was submitted to chromatography (SiO₂,heptane/ethyl acetate 2:1) to give the following: RSC8-1 (76 mg; 22%),2-bromomethyl-3-octylthioprop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(72 mg; 24%) having [α]_(D) -7° (c 0.6, CHCl₃) and the starting materialDIB-6 (34 mg).

The 2-bromomethyl compound above (57 mg, 0.062 mmol) was dissolved indimethylformamide (1.5 ml) and methyl 11-mercaptoundecanoate (22 mg,0.093 mmol) and cesium carbonate (30 mg) were added at room temperature.The mixture was stirred for 15 h, worked up with dichloromethane andwater and the organic phase was dried (Na₂ SO₄) and concentrated. Theresidue was chromatographed (SiO₂, hexane:ethyl acetate) to giveRSC10EC8 (59 mg) which had [α]_(D) ²⁵ -4° (c 1.8, CDCl₃).

NMR-Spectrum (CDCl₃, Me₄ Si): δ (ppm)=5.37 (dd, 1H, J3.5=1.0 Hz, H-4'),5.22 (t, 1H, J₂,3 =9.3 Hz, H-2), 5.13 (dd, 1H, J_(2'),3' =10.5 Hz,H-2'), 4.97 (dd, 1H, J_(3'),4' =3.3 Hz, H-3'), 4.91 (dd, 1H, J₃,4 =7.7Hz, H-3), 4.50, 4.48 (two d, each 1H, J₁,2 =7.8 Hz, J₁,2 =7.8 Hz,H-1,1'), 3.69 (s, 3H, OMe), 0.91 (t, 3H, J=6.6 Hz, --CH₂ --CH₃).

                  TABLE 2                                                         ______________________________________                                         ##STR23##                                                                    Compound                                                                      no.     R'.sub.1                                                                              R'.sub.2                                                                             R'.sub.3                                                                           R'.sub.4                                                                            R'.sub.5                                                                             R'.sub.6                             ______________________________________                                        R.sub.a = R.sub.b = (CH.sub.2).sub.15 CH.sub.3                                RSC16-1 OAc.sup.a                                                                             H     OAc  OAc    H      CH.sub.2 OAc                         RSC16-2 OAc     H     OAc  H      OAc    CH.sub.2 OAc                         RSC16-3 OAc     H     OAc  OAc    H      COOCH.sub.3                          RSC16-4 NPhth.sup.b                                                                           H     OAc  OAc    H      CH.sub.2 OAc                         RSC16-5 OAc     H     OAc  OAc    H      H                                    RSC16-6 OAc     H     OAc  GalAcβ.sup.c                                                                    H      CH.sub.2 OAc                         RSC16-7 OAc     H     OAc  H      GalAcα.sup.d                                                                   CH.sub.2 OAc                         RSC16-8 OH      H     OH   OH     H      CH.sub.2 OH                          RSC16-9 OH      H     OH   H      OH     CH.sub.2 OH                          RSC16-10                                                                              OH      H     OH   OH     H      COOH                                 RSC16-11                                                                              NHAc    H     OH   OH     H      CH.sub.2 OH                          RSC16-12                                                                              OH      H     OH   OH     H      H                                    RSC16-13                                                                              OH      H     OH   GalOHβ.sup.e                                                                    H      CH.sub.2 OH                          RSC16-14                                                                              OH      H     OH   H      GalOHα.sup.f                                                                   CH.sub.2 OH                          R.sub.a = R.sub.b = (CH.sub.2).sub.17CH.sub.3                                 RSC18-1 OAc     H     OAc  GalAcβ                                                                          H      CH.sub.2 OAc                         RSC18-2 OH      H     OH   GalOHβ                                                                          H      CH.sub.2 OH                          R.sub.a = R.sub.b = (CH.sub.2).sub.7CH.sub.3                                  RSC8-1  OAc     H     OAc  GalAcβ                                                                          H      CH.sub.2 OAc                         RSC8-2  OH      H     OH   GalOHβ                                                                          H      CH.sub.2 OH                          R.sub.a = R.sub.b = (CH.sub.2).sub.10COOCH.sub.3                              RSC10E-1                                                                              OAc     H     OAc  GalAcβ                                                                          H      CH.sub.2 OAc                         RSC10E-2                                                                              OH      H     OH   GalOHβ                                                                          H      CH.sub.2 OH                          R.sub.a = (CH.sub.2).sub.10COOCH.sub.3,                                       R.sub.b = (CH.sub.2).sub.7CH.sub.3                                            RSC10EC8                                                                              OAc     H     OAc  GalAcβ                                                                          H      CH.sub.2 OAc                         ______________________________________                                         .sup.a Ac = acetyl;                                                           .sup.b Phth = phthaloyl;                                                      .sup.c GalAcβ = 2,3,4,6-tetra-Oacetyl-β-Dgalactopyranosyl;          .sup.d GalAcα = 2,3,4,6-tetra-Oacetyl-α-galactopyranosyl;         .sup.e GalOHβ = β-Dgalactopyranosyl;                                .sup.f GalOHα = α-Dgalactopyranosyl.                         

EXAMPLE 3 Preparation of bis-sulfoxide and bis-sulfone glycosides

(a) A fully acetylated bis-sulfide glycoside (0.5 mmol) was dissolved inethyl acetate (20 ml) and cooled (-25°). m-Chloroperbenzoic acid (2mmol) was added and the mixture was stirred until the starting materialhad been consumed (30-60 min; checked by TLC). The bis-sulfone formed(see Table 4) was purified on a small column of alumina and thenisolated by chromatography. Deacetylation was performed as in Example 2.Using the same procedure as above, but with 1 mmol of m-chloroperbenzoicacid, permits the isolation of the corresponding bis-sulfoxide (seeTable 3). The following compounds may be prepared:

3-Hexadecylsulfoxy-2-hexadecylsulfoxymethyl-prop-1-yl2,3,4,6-tetra-acetyl-β-D-glucopyranoside (RSOC161). From RSC166. Yield:38%. [α]_(D) ²⁵ -11° (c 1, CDCl₃). IR λ1755, 1050 cm⁻¹.

NMR-spectrum (CDCl₃, Me₄ Si): δ (ppm)=complete agreement with adiastereomeric mixture as expected of sulfoxides. Sharp signals were:1.26 (bs, 56H, CH₂), 0.88 (t, 3H, J 6.3 Hz, CH₃)

Analysis: Calculated for C₅₀ H₉₂ O₁₂ S₂ C 63.3 H 9.77 Found: C 62.9 H9.86

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl2,3,4,6-tetra-O-acetyl-β-D-glycopyranoside (RSO₂ C16-1). From RSC16-1.Yield: 80%. [α]_(D) ²³ =-5.6° (c=0.7 in CDCl₃). NMR-Specrum (CDCl₃,TMS): δ (ppm)=5.21 (t, 1 H, J₂,3 =9.5 Hz, H-3), 5.05 (t, 1 H, J₃,4 =J₄,5=10.0 Hz, H-4), 4.97 (dd, 1 H, H-2), 4.54 (d, 1 H, J₁,2 =8.1 Hz, H-1),4.27, 4.13 (ABq with further coupling, each 1 H, J_(AB) =12.5 Hz, J₅,6=4.9 Hz, J_(5'),6' =2.4 Hz, H-6,6'), 3.70 (m, 1 H, H-5).

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (RSO₂ C16-2). From RSC16-2.NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.39 (dd, 1 H, J₄.5 =1.0 Hz, H-4),5.15 (dd, 1 H, J₂,3 =10.5 Hz, H-2), 5.01 (dd, 1 H, J₃,4 =3.4 Hz, H-3),4.50 (d, 1H, J₁,2 =7.7 Hz, H-1).

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl-.beta.-D-glucopyranoside(RSO₂ C16-6). From RSC16-6. Yield: 69%. [α]_(D) ²³ =-6.7° c) =0.8 inCDCl₃). NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.35 (dd, 1 H, J_(4'),5' =1Hz, H-4'), 5.19 (t, 1 H, J₂,3 =9.4 Hz, H-2), 5.11 (dd, 1 H, J_(2'),3'=10.1 Hz, H-2'), 4.96 (dd, 1 H, J_(3'),4' =3.2 Hz, H-3'), 4.88 (dd, 1 H,J₃,4 =7.9 Hz, H-3), 4.50, 4.48 (two d, each 1 H, J₁,2 =J_(1'),2' =7.6Hz, H-1 and H-1').

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(RSO₂ C16-7). From RSC16-7. Yield: 99%. [α]_(D) ²³ =+47.2° (c=0.6 inCDCl₃). NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.58 (dd, 1 H, J_(4'),5' =1Hz, H-4'), 5.39 (dd, 1 H, J_(2'),3' =11 Hz, H-2'), 5.21 (dd, 1 H,J_(3'),4' =3.4 Hz, H-3'), 5.15 (dd, 1 H, J₂,3 =11 Hz, H-2), 4.97 (d, 1H, J_(1'),2' =3.9 Hz, H-1'), 4.79 (dd, 1 H, J₃,4 =2.7 Hz, H-3), 4.51 (d,1 H, J₁,2 =7.8 Hz, H-1).

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-ylβ-D-glucopyranoside (RSO₂ C16-8). From RSO₂ C16-1. [α]_(D) ²³ =+3.9°(c=0.9 in CMD). NMR-Spectrum (CMD, TMS): δ (ppm)=4.34 (d, 1 H, J₁,2 =7.3Hz, H-1), 0.89 (t, 6 H, J=6.8 Hz, CH₂ --CH₃),

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-ylβ-D-galactopyranoside (RSO₂ C16-9). From RSO₂ C16-2.

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSO₂ C16-13). From RSO₂C16-6. [α]_(D) ²³ =-1° (c=0.5 in CMD). NMR-Spectrum (TMS): δ (ppm)=4.39,4.31 (d, each 1 H, J=7.6 and 7.8 Hz, H-1,1'), 2.71 (d, 4H, J=6.6 Hz,CH--CH₂ --SO₂), 2.53 (t, 4H, J=7.3 Hz, SO₂ --CH₂ --CH₂).

3-Hexadecylsulfonyl-2-hexadecylsulfonylmethyl-prop-1-yl4-O-α-D-galactopyranosyl-β-D-galactopyranoside (RSO₂ C16-14). From RSO₂C16-7. [α]_(D) ²³ =+27.4° (c=0.8 in CMD). ¹³ C-NMR-Spectrum (CMD, TMS: δ(ppm)=4.34, (d, 1 H, J₁,2 =7.3 Hz, H-1), 0.89 (t, 1 H, J=6.8 Hz, CH₂--CH₃). 3-(10-Methoxycarbonyldecylsulfonyl)2-(10-methoxycarbonyldecylsulfonylmethyl)-prop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSO₂ C10E-1) and3-(10-methoxycarbonyldecylsulfonyl)-2-octylsulfonylmethyl-prop-1yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(RSO₂ C10EC8-1). DIB-6 (2.6 g, 3 mmol) was dissolved in drydimethylformamide (29 ml) and methyl 11-mercaptoundecanoate (2 ml) wasadded, followed by cesium carbonate (1.5 g). The reaction was monitoredby TLC. After 40 h at 20°, water was added and the mixture was extractedwith dichloromethane. Drying and evaporation of the solvents left aresidue that was dissolved in ethyl actate (80 ml) andm-chloroperbenzoic acid (12.15 mmol) was added. After 18 h, the mixturewas filtered through a column of aluminum oxide (70 g) withdichloromethane (300 ml). The solvents were removed and 10% of theresidue was chromatographed (SiO₂ ; hexane/ethyl acetate, 2:3) to give2-bromomethyl-3-(10-methoxycarbonyldecylsulfonyl)-prop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(1.00 g, 36%) with [α]_(D) -6° (c 0.7, CHCl₃), followed by RSO₂ C10E-1(1.01 g, 31%) with [α]_(D) -7° (c 1.1, CHCl₃)

NMR spectrum (CDCL₃, TMS): δ (ppm)=4.48, 4.50 (d, 1H each, J 7.6 and 7.8Hz, H-1, H-1'), 3.66 (s, 3H, OCH₃).

The 2-bromomethyl compound above (820 mg, 0.79 mmol was dissolved indimethyl formamide (20 ml) and octanethiol (174 mg, 1.19 mmol) wasadded, followed by cesium carbonate (240 mg). After 20 h, the mixturewas partitioned between dichloromethane (120 ml) and water (100 ml) andthe aqueous phase was extracted with dichloromethane (50 ml). Thecombined organic phases were dried (Na₂ SO₄) and concentrated and theresidue was submitted to chromatography (SiO₂, hexane/ethyl acetate 1:1)to give pure3-(10-methoxycarbonyldecylsulfonyl)-2-octylthiomethyl-prop-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(830 mg, 96%) with [α]_(D) -5° (c 0.9, CHCl₃) NMR-spectrum (CDCl₃, TMS):δ (ppm)=4.48, 4.46 (m, 1H each, H1, H-1'), 3.67 (s, 3H, OCH₃), 0.88 (t,3H, J6.9 Hz, CH₂ --CH₃)

This sulfone-sulfide (800 mg, 0.74 mmol) was dissolved in ethyl acetate(25 ml) and m-chloroperbenzoic acid (1.85 mmol) was added. After 18 h,the mixture was concentrated and then dissolved in dichloromethane andfiltered through a column of alumina (15 mg). Evaporation of thesolvents gave pure RSO₂ C10EC8-1 (667 mg, 80%) with [α]_(D) -14° (c 0.8,CHCl₃).

NMR-spectrum (CDCl₃, TMS): δ (ppm)=4.49, 4.47 (d, 1H each, J 7.8 and 7.8Hz, H-1, H1'), 3.66 (s, 3H, OCH₃), 0.87 (t, 3H, J 6.4 Hz, CH₂ --CH₃)

3-(10-Methoxycarbonyldecylsulfonyl)-2-(10-methoxycarbonyldecylsulfonylmethyl)-prop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSO₂ C10E-2). RSO₂ C10E-1was conventionally deacetylated (MeOH/MeONa) to give RSO₂ C10E-2 with[α]_(D) -3° (c 0.8, CMH).

3-(10-Methoxycarbonyldecylsulfonyl)-2-octylsulfonylmethyl-prop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSO₂ C10EC8-2). RSO₂C10EC8-1 was conventionally deacetylated (MeOH/MeONa) to give RSO₂C10EC8-2 with [α]_(D) -1° (c 0.9, CMH).3-(10-Carboxydecylsulfonyl)-2-(10-carboxydecylsulfonylmethyl)-prop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSO₂ C10A).

RSO₂ C10E-2 (13 mg, 0.014 mmol) was added to sodium hydroxide solution(0.01M, 10 ml) and heated at 100° for 30 min. The mixture was cooled andacetic acid (1 drop) was added. The solvent was removed to give RSO₂C10A, contaminated with sodium acetate.

3-(10-Carboxydecylsulfonyl)-2-octylsulfonylmethyl-prop-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (RSO₂ C10AC8). RSO₂C10EC8-2 was treated with sodium hydroxide solution as above to giveRSO₂ C10AC8, contaminated with sodium acetate.

(b) 2-(Hexadecylsulfonyl)ethyl2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside. 2-Bromoethyl2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (Dahmen et al. Carbohydr.Res., 116 (1983)) (540 mg, 1.19 mmol), hexadecanethiol (383 mg, 1.49mmol), cesium carbonate (292 mg, 0.89 mmol) and dimethylformamide (5 ml)was stirred overnight. Dichloromethane (75 ml) and water (40 ml) wereadded. The aqueous phase was extracted with dichloromethane (2×25 ml),the combined organic phases were dried (Na₂ SO₄) and concentrated.Chromatography (SiO₂ ; ethylacetate: hexane) gave pure2-(hexadecylthio)ethyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (480mg, 0.76 mmol, 64%), which was dissolved in ethyl acetate (12 ml) andtreated with m-chloroperbenzoic acid (1.71 mmol). After 4 hours thesolvents were removed and the residue was dissolved in dichloromethaneand filtered through alumina (10 g) to give the pure sulfone lipid (495mg, 98%). [α]_(D) ²³ =-8.7° (c=0.9 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.21 (t, 1 H, J₃,4 =9.5 Hz, H-3),5.07 (t, 1 H, J₄,5 =9.7 Hz, H-4), 5.00 (dd, 1 H, J₂,3 =9.5 Hz, H-2),4.57 (d, 1 H, J₁,2 =8.1 Hz, H-1), 4.28 , 4.14 (ABq with furthercoupling, each 1 H, J_(AB) =12.5 Hz, J₅,6 =4.88 Hz, J₅,6', =2.44 Hz,H-6,6'), 3.72 (m, 1 H, H-5). 2-(Hexadecylsulfonyl)ethylβ-D-glucopyranoside. The sulfone lipid above (440 mg) was dissolved indichloromethane (45 ml), and methanolic sodium methoxide (30 ml; from 1mg Na) was added. After 24 hours (TLC showed complete deacetylation),acetic acid (1 drop) was added and the solvents were removed, finally at<0.1 Torr, to give the deacetylated material (320 mg, 97%), contaminatedwith a small amount of sodium acetate. [α]_(D) ²³ =-10,5° (c=1,0 inCMD). NMR-Spectrum (CMD, TMS): δ (ppm)=4.36 (d, 1 H, J₁,2 =7.8 Hz, H-1),0.89 (t, 3 H, J=6.8 Hz, CH₂ -CH₃).

                                      TABLE 3                                     __________________________________________________________________________     ##STR24##                                                                    Compound no.                                                                           R'.sub.1                                                                          R'.sub.2                                                                         R'.sub.3                                                                         R'.sub.4                                                                           R'.sub.5                                                                             R'.sub.6                                       __________________________________________________________________________    R = (CH.sub.2).sub.15 CHS                                                     RSOC16-1 OAc.sup.a                                                                         H  OAc                                                                              OAc  H      CH.sub.2 OAc                                   RSOC16-2 OAc H  OAc                                                                              H    OAc    CH.sub.2 OAc                                   RSOC16-3 OAc H  OAc                                                                              OAc  H      COOCH.sub.3                                    RSOC16-4 NPhth.sup.b                                                                       H  OAc                                                                              OAc  H      CH.sub.2 OAc                                   RSOC16-5 OAc H  OAc                                                                              OAc  H      H                                              RCOC16-6 OAc H  OAc                                                                              GalAcβ.sup.c                                                                  H      CH.sub.2 OAc                                   RSOC16-7 OAc H  OAc                                                                              H    GalAcα.sup.d                                                                   CH.sub.2 OAc                                   RSOC16-8 OH  H  OH OH   H      CH.sub.2 OH                                    RSOC16-9 OH  H  OH H    OH     CH.sub.2 OH                                    RSOC16-10                                                                              OH  H  OH OH   H      COOH                                           RSOC16-11                                                                              NHAc                                                                              H  OH OH   H      CH.sub.2 OH                                    RSOC16-12                                                                              OH  H  OH OH   H      H                                              RSOC16-13                                                                              OH  H  OH GalOHβ.sup.e                                                                  H      CH.sub.2 OH                                    RSOC16-14                                                                              OH  H  OH H    GalOHα.sup.f                                                                   CH.sub.2 OH                                    R = (CH.sub.2).sub.17CH.sub.3                                                 RSOC18-1 OAc H  OAc                                                                              GalAcβ                                                                        H      CH.sub.2 OAc                                   RSOC18-2 OH  H  OH GalOHβ                                                                        H      CH.sub.2 OH                                    R = (CH.sub.2).sub.7CH.sub.3                                                  RSOC8-1  OAc H  OAc                                                                              GalAcβ                                                                        H      CH.sub.2 OAc                                   RSOC8-2  OH  H  OH GalOHβ                                                                        H      CH.sub.2 OH                                    R = (CH.sub.2).sub.10COOCH.sub.3                                              RSOC10E-1                                                                              OAc H  OAc                                                                              GalAcβ                                                                        H      CH.sub.2 OAc                                   RSOC10E-2                                                                              OH  H  OH GalOHβ                                                                        H      CH.sub.2 OH                                    __________________________________________________________________________     .sup.a Ac = acetyl;                                                           .sup.b Phth = phthaloyl;                                                      .sup.c GalAcβ = 2,3,4,6-tetra-Oacetyl-β-D-galactopyranosyl;          .sup.d GalAcα = 2,3,4,6-tetra-Oacetyl-α-D-galactopyranosyl;      .sup.e GalOHβ = β-D-galactopyranosyl;                               .sup.f GalOHα =α-D-glactopyranosyl.                          

                                      TABLE 4                                     __________________________________________________________________________     ##STR25##                                                                    Compound no.                                                                             R'.sub.1                                                                          R'.sub.2                                                                         R'.sub.3                                                                         R'.sub.4                                                                           R'.sub.5                                                                           R'.sub.6                                       __________________________________________________________________________    R.sub.a = R.sub.b = (CH.sub.2).sub.15 CH.sub.3                                RSO.sub.2 C16-1                                                                          OAc.sup.a                                                                         H  OAc                                                                              OAc  H    CH.sub.2 OAc                                   RSO.sub.2 C16-2                                                                          OAc H  OAc                                                                              H    OAc  CH.sub.2 OAc                                   RSO.sub.2 C16-3                                                                          OAc H  OAc                                                                              OAc  H    COOCH.sub.3                                    RSO.sub.2 C16-4                                                                          NPhth.sup.b                                                                       H  OAc                                                                              OAc  H    CH.sub.2 OAc                                   RSO.sub.2 C16-5                                                                          OAc H  OAc                                                                              OAc  H    H                                              RSO.sub.2 C16-6                                                                          OAc H  OAc                                                                              GalAcβ.sup.c                                                                  H    CH.sub.2 OAc                                   RSO.sub.2 C16-7                                                                          OAc H  OAc                                                                              H    GalAcα.sup.d                                                                 CH.sub.2 OAc                                   RSO.sub.2 C16-8                                                                          OH  H  OH OH   H    CH.sub.2 OH                                    RSO.sub.2 C16-9                                                                          OH  H  OH H    OH   CH.sub.2 OH                                    RSO.sub.2 C16-10                                                                         OH  H  OH OH   H    COOH                                           RSO.sub.2 C16-11                                                                         NHAc                                                                              H  OH OH   H    CH.sub.2 OH                                    RSO.sub.2 C16-12                                                                         OH  H  OH OH   H    H                                              RSO.sub.2 C16-13                                                                         OH  H  OH GalOHβ.sup.e                                                                  H    CH.sub.2 OH                                    RSO.sub.2 C16-14                                                                         OH  H  OH H    GalOHα.sup.f                                                                 CH.sub.2 OH                                    R.sub.a = R.sub.b = (CH.sub.2).sub.17 CH.sub.3                                RSO.sub.2 C18-1                                                                          OAc H  OAc                                                                              GalAcβ                                                                        H    CH.sub.2 OAc                                   RSO.sub.2 C18-2                                                                          OH  H  OH GalOHβ                                                                        H    CH.sub.2 OH                                    R.sub.a = R.sub.b = (CH.sub.2).sub.7CH.sub.3                                  RSO.sub.2 C8-1                                                                           OAc H  OAc                                                                              GalAcβ                                                                        H    CH.sub.2 OAc                                   RSO.sub.2 C8-2                                                                           OH  H  OH GalOHβ                                                                        H    CH.sub.2 OH                                    R.sub.a  = R.sub.b = (CH.sub.2).sub.10 COOCH.sub.3                            RSO.sub.2 C10E-1                                                                         OAc H  OAc                                                                              GalAcβ                                                                        H    CH.sub.2 OAc                                   RSO.sub.2 C10E-2                                                                         OH  H  OH GalOHβ                                                                        H    CH.sub.2 OH                                    R.sub.a  = R.sub.b = (CH.sub.2).sub.10 COOH                                   RSO.sub.2 C10A                                                                           OH  H  OH GalOHβ                                                                        H    CH.sub.2 OH                                    R.sub.a = (CH.sub.2).sub.10 COOCH.sub.3,                                      R.sub.b  = (CH.sub.2).sub.7 CH.sub.3                                          RSO.sub.2 C10EC8-1                                                                       OAc H  OAc                                                                              GalAcβ                                                                        H     CH.sub.2 OAc                                  RSO.sub.2 C10EC8-2                                                                       OH  H  OH GalOHβ                                                                        H    CH.sub.2 OH                                    R.sub.a  = (CH.sub.2).sub.10 COOH,                                            R.sub.b  = (CH.sub.2).sub.7 CH.sub.3                                          RSO.sub.2 C10AC8                                                                         OH  H  OH GalOHβ                                                                        H     CH.sub.2 OH                                   __________________________________________________________________________     .sup.a Ac = acetyl;                                                           .sup.b Phth = phthaloyl;                                                      .sup.c GalAcβ = 2,3,4,6-tetra-Oacetyl-β-D-galactopyranosyl;         .sup.d GalAcα = 2,3,4,6-tetra-Oacetyl-α-D-galactopyranosyl;       .sup.e GalOHβ = β-D-galactopyranosyl;                               .sup.f GalOHα = α-D-galactopyranosyl.                        

EXAMPLE 4

The use of 2-bromomethylallyl glycosides with sulfur, nitrogen andoxygen nucleophiles A DIB glycoside (1 mmol) was dissolved in ethylacetate (10 ml) and diazabicycloundecane (DBU; 2 mmol) was addeddropwise. After ca. 5 h (crystalline DBU-hydrobromide had been formed),1 mmol of an appropriate thiol was added. Alternatively, an equivalentamount of an appropriate amine or alcohol may be added. The reaction wasmonitored by TLC, which showed that the intermediate allylic bromideglycoside was consumed and that a new product was formed. The solidmaterial was removed and the residue was subjected to chromatography,which gave the pure product. Deacetylation was performed as in Example2. The following compounds may be prepared:

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (ARSC2E-1). From DlB-1.

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl β-D-glucopyranoside(ARSC2E-2). From ARSC2E-1.

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (ARSC2E-3). From DlB-2.

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl β-D-galactopyranoside(ARSC2E-4). From ARSC2E-3.

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(ARSC2E-5). From DlB-6. Yield: 43%. [α]_(D) ²³ =-11.5° (c=0.8 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): β (ppm)=5.35 (dd, 1 H, J_(4'),5' =0.7 Hz,H-4'), 5.20 (t, 1 H, J₂,3 =9.3 Hz, H-2), 5.12, 5.07 (bs, each 1 H,═CH₂), 5.11 (dd, 1 H, J_(2'),3' =9.8 Hz, H-2'), 4.95 (dd, 1 H, J_(3'),4'=3.4 Hz, H-3'), 4.93 (t, 1 H, J₃,4 =8.1 Hz, H-3), 4.51, 4.48 (d, each 1H, J₁,2 =7.8 Hz, H-1,1'), 4.37, 4.17 (ABq, each 1 H, J_(Ab) = 12.0 Hz,O--CH₂ --C═), 3.70 (s, 3 H, OCH₃), 3.17, 3.14 (ABq, each 1 H, ═C--CH₂--S).

2-(2-methoxycarbonylethylthiomethyl)prop-2-en-1-yl4-O-β-D-galactopyranosyl-β-D-glycopyranoside (ARSC2E-6). From ARSC2E-5.

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(ARSC2E-7). From DlB-7. Yield: 44%. [α]_(d) =+53° (c=0.8 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.57 (dd, 1 H, J_(4'),5' =1.2 Hz,H-4'), 5.38 (dd, 1 H, J_(2'),3' =11.0 Hz, H-2'), 5.21 (dd, 1 H, J₂,3=10.8 Hz, H-2), 5.20 (dd, 1 H, J_(3'),4' =3.4 Hz, H-3'), 5.16, 5.07 (bs,each 1 H, ═CH₂), 5.00 (d, 1 H, J_(1'),2' =3.7 Hz, H-1'), 4.82 (dd, 1 H,J₃,4 =2.9 Hz, H-3), 4.51 (d, 1 H, J;hd 1,2=7.6 Hz, H-1), 4.41, 4.20(ABq, each 1 H, J_(AB) =12.3 Hz, O--CH₂ --C═), 3.70 (s, 3 H, OCH₃),3.21, 3.17 (ABq, each 1 H, J_(AB) =14.1 Hz, ═C--CH₂ --S).

2-(2-Methoxycarbonylethylthiomethyl)prop-2-en-1-yl4-O-α-D-galactopyranosyl-β-D-galactopyranoside (ARSC2E-8). FromARSC2E-7.

2-(Hexadecylthiomethyl)prop-2-en-1-yl2,3,4-tri-O-acetyl-β-D-xylopyranoside (ARSC16-1). From DlB-5. Yield:42%. NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.20-4.88 (m, 3 H, H-3,2,4),5.09, 5.01 (bs, each 1 H, ═CH₂), 4.51, (d, 1 H, J₁,2 =6.9 Hz, H-1), 4.374.13 (ABq, each 1 H, J_(AB) =12.4 Hz, C--CH₂ --O), 4.16-4.08 (m, 1 H,H-5), 3.35 (dd, 1 H, J₄,5' =8.6 Hz, J₅,5' =11.8 Hz, H-5'), 3.13 (s, 2 H,═C--CH₂ --S), 2.35 (t, 2 H, J=7 Hz, CH₂ --CH₂ --S).

2-(Hexacedylthiomethyl)prop-2-en-1-yl β-D-xylopyranoside (ARSC16-2).From ARSC16-1.

2-Hexadecylthiomethyl)prop-2-en-1-yl2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (ARSC16-3). From DlB-2.

2-(Hexadecylthiomethyl)prop-2-en-1-yl β-D-galactopyranoside (ARSC16-4).From ARSC16-3.

2-(Hexadecylthiomethyl)prop-2-en-1-yl2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (ARSC16-5). From DlB-1.Yield: 50%. [α]_(D) ²³ =-14.7° (c=1.4 in CDCl₃).

NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.21 (t, 1 H, J₂,3 =J₃,4 =9.4 Hz,H-3), 5.10 (t, 1 H, J₄,5 =9.8 Hz, H-4), 5.097, 5.03 (s, each 1 H, ═CH₂),5.04 (t, 1 H, H-2), 4.54 (d, 1 H, J₁,2 =8.0 Hz, H-1), 4.41, 4.20 (ABq,each 1 H, J_(AB) =15.0 Hz, O--CH₂ --C═), 4.27, 4.15 (ABq with furthercoupling, each 1 H, J_(AB) =12.0 Hz, J₅,6 =4.6 Hz, J₅,6' =2.4 Hz,H-6,6'), 3.69 (octet, 1 H, H-5), 3.15, 3.11 (ABq, each 1 H, J_(AB) =13.9Hz, ═C--CH₂ --S), 2.36 (t, 2 H, J=7 Hz, S--CH₂ --CH₂).

2-(Hexadecylthiomethyl)prop-2-en-1-yl β-D-glucopyranoside (ARSC16-6).From ARSC16-5.

2-(Hexadecylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α-D-glucopyranoside(ARSC16-7). From DlB-6. Yield: 46%. [α]_(D) ²³ =-11.0° (c=1.4 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.34 (dd, 1 H, J_(4'),5' =1.0 Hz,H-4'), 5.20 (t, 1 H, J₂,3 =9.0 Hz, H-2), 5.11 (dd, 1 H, J_(2'),2' =-10.1Hz, H-2'), 5.08, 5.02 (bs, each 1 H, ═CH₂), 4.95 (dd, 1 H, J_(3'),4'=3.7 Hz, H-3'), 4.93 (t, 1 H, J₃,4 =8.1 Hz, H-3), 4.51, 4.48 (d, each 1H, J₁,2 =7.8 Hz, H-1,1), 4.38, 4.16 (ABq, each 1 H, J_(AB) = 12.0 Hz,O--CH₂ --C═), 3.14, 3.10 (ABq, each 1 H, J_(AB) =14.3 Hz, ═C--CH₂ --S),2.37 (t, 1 H, J=7.4 Hz, S--CH₂ --CH₂).

2-(Hexadecylthiomethyl)prop-2-en-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (ARSC16-8). From ARSC16-7.

2-(Hexadecylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(ARSC16-9). From DlB-7. Yield 50%. [α]_(D) ²³ =+56,4° (c=0.5 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.57 (dd, 1 H, J_(4'),5' =1 Hz, H-4'), 5.38 (dd, 1 H, J_(2'),3' =11.0 Hz, H-2'), 5.21 (dd, 1 H, J₂,3 =10.7Hz, H-2), 5.20 (dd, 1 H, J_(3'),4' =3.2 Hz, H-3'), 5.12, 5.03 (bs, each1 H, ═CH₂), 5.00 (d, 1 H, J_(1'),2' =3.7 Hz, H-1'), 4.82 (dd, 1 H, J₃,4=2.7 Hz, H-3), 4.51 (d, 1 H, J₁,2 =7.8 Hz, H-1), 4.42, 4.20 (ABq, each 1H, J_(AB) =12.3 Hz, O--CH₂ --C═), 3.17, 3.14 (ABq, each 1 H, J_(AB)=14.2 Hz, ═C--CH₂ --S), 2.39 (t, 2 H, J=7.3 Hz, S--CH₂ --CH₂).2-(Hexadecylthiomethyl)prop-2-en-1-yl4-O-α-D-galactopyransoyl-β-D-galactopyranoside (ARSC16-10). FromARSC16-9.

2-(10-Methoxycarbonyldecylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside(ARSC10E-1). From DlB-6. Yield: 52%. [α]_(D) ²³ =-8.9° (c=CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.35 (dd, 1 H, J_(4'),5' =0.7 Hz,H-4'), 5.20 (t, 1 H, J₂,3 =9.0 Hz, H-2), 5.11 (dd, 1 H, J_(2'),3' =-10.5Hz, H-2'), 5.08, 5.02 (bs, each 1 H, ═CH₂), 4.95 (dd, 1 H, J_(3'),4'=3.5 Hz, H-3'), 4.94 (t, 1 H, J₃,4 =8,5 Hz, H-3), 4.50, 4.48 (d, each 1H, J₁,2 =J_(1'),2' =7,8 Hz, h-1,1'), 4.38, 4.16 (ABq, each 1 H, J_(AB)=12.0 Hz, O--CH₂ --C═), 3.67 (s, 3 H, OCH₃), 3.14, 3.10 (ABq, each 1 H,J_(AB) =14.5 Hz, ═C--CH₂ --S), 2.37 (t, 2 H, J=7.5 Hz, S--CH₂ --CH₂),2.30 (t, 2 H, J=7.5 Hz, CH₂ --COO).

2-(10-Methoxycarbonyldecylthiomethyl)prop-2-en-1-yl4-O-β-D-galactopyranosyl-β-D-glucopyranoside (ARSC10E-2). FromARSC10E-1.

2-(10-Methoxycarbonyldecylthiomethyl)prop-2-en-1-yl2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside(ARSC10E-3). From DlB-7. Yield: 51%. [α]_(D) ²³ =+55° (c=1.1 in CDCl₃).NMR-Spectrum (CDCl₃, TMS): δ (ppm)=5.57 (dd, 1 H, J_(4'),5' =1.2 Hz,H-4'), 5.38 (dd, 1 H, J_(2'),3' =11.0 Hz, H-2'), 5.21 (dd, 1 H, J₂,3=10.5 Hz, H-2), 5.20 (dd, 1 H, J_(3'),4' =3.2 Hz, H-3'), 5.12, 5.03 (bs,each 1 H, ═CH₂), 5.00 (d, 1 H, J_(1'),2' =3.7 Hz, H-1'), 4.82 (dd, 1 H,J₃,4 =2.9 Hz, H-3), 4.51 (d, 1 H, J₁,2 =7.8 Hz, H-1), 4.42 4.20 (ABq,each 1 H, J_(AB) =12.7 Hz, O--CH₂ --C═), 3.67 (s, 3 H, OCH₃), 3.17, 3.14(ABq, each 1 H, J_(AB) =14.2 Hz, ═C--CH₂ --S), 2.39 (t, 2 H, J₇.3 Hz,S--CH₂ CH₂), 2.30 (t, 2 H, J=7.8 Hz, CH₂ COO).

EXAMPLE 5 Preparation of neo-glycoconjugates

(a) Glycosides with one or two terminal ester groups (RSO₂ C10E-2, RSO₂C10EC8-2, and ARSC2E-3) were transformed into the corresponding acylazides, essentially as described by Dahmen et al. (Carbohydr. res. 129(1984) in their preparation of neo-glycoconjugates. The reaction mixturecontaining the acyl azide in methylsulfoxide was added dropwise to theamino-group-containing carrier in Na₂ B₄ O₇ -RHCO₃ buffer (see Dahmen etal.) at pH 9.0-9.3 and the resulting mixture was stirred over night. Thefollowing conjugates were prepared. RSO₂ C10EC8-2.BSA. From RSO₂C10EC8-2 (50 mg, 0.07 mmol) and bovine serum albumin (BSA, 65 mg). Thereaction mixture was dialyzed (4×5 l distilled water) and the residuewas freeze-dried to give the neo-glycoprotein. The degree of binding(number of sugar units per protein molecule) was 21 as determined bydifferential sulfur combustion analysis. ARSC2E-3.BSA. ARSC2E-2 wasconventionally deacetylated to give ARSC2E-3 (36 mg, 0.07 mmol) whichwas coupled to BSA (65 mg) as above. Freeze-drying gave theneo-glycoprotein which had a degree of binding of 18 as determined bydifferential sulfur combustion analysis.

RSO₂ C10EC8-2. spermidine. From RSO₂ C10EC8-2 (94 mg, 0.13 mmol) andspermidinium trichloride (12.1 mg, 0.067 mmol). The crude productseparated as a gel and was isolated by filtration of the reactionmixture and then chromatographed (SiO₂, CMH, 65/35/10) to give the pureconjugate. RSO₂ C10E-2.SiO₂. From RSO₂ C10E-2 (50 mg, 0.054 mmol) andaminated silica gel (166 mg, Sperisorb 5 μm, 0.6 mmol amino groups/g;Phase Sep, Deeside Ind. Est., Queensferry, Clwyd, UK). The resultingglycoconjugate was washed twice with water, methanol and dichloromethaneby centrifugation. Drying under vacuum gave 154 mg of the pureglycoconjugate. The degree of binding was 0.13 mmol of the sugarhapten/per g of the conjugate as determined by sulfur combustionanalysis.

ARSC2E-3.SiO₂ was conventionally deacetylated to give ARSC2E-3 (46 mg,0.09 mmol) which was coupled to the aminated silica gel (95 mg), workedup and purified as above to give 88 mg of the pure glycoconjugate. Thedegree of binding was 0.19 mmol of the sugar hapten/per g of theconjugate as determined by sulfur combustion analysis.

(b) ARSC3-SiO₂. A fully acetylated DlB glycoside (DlB-6, 85 mg, 0.1mmol) was dissolved in dry ethyl acetate (1.5 ml) anddiazabicycloundecane (46 mg, 0.3 mmol, 45 μl) was added. The mixture wasstirred for 3 h and thiolated silica gel (114 mg, prepared by treatingLichrosorb, Merck, 10 μm, ˜300 m² /g, 3-trimethoxysilylpropan-1-thiol;˜0.9 mmol thiol/g of product) was added. After 2 h, the sugar wasconsumed (according to TLC analysis) and the conjugate was washed withdichloromethane, water and methanol on a glass filter. The conjugate wasdeacetylated with methanolic sodium methoxide (0.02M, 1 ml) over night,washed with water, methanol, dichloromethane and ether, and dried. Thedegree of binding was 0.23 mmol of the sugar hapten/per g of theconjugate as determined by carbon combustion analysis. This means that˜25% of the available thiol groups had reacted.

EXAMPLE 6 Preparation of multi-dentate glycosides

A fully acetylated DlB glycoside (1 mmol), an alkyldithiol (1 mmol),cesium carbonate (1 mmol) and dimethyl-formamide (2 mmol) is stirred atroom temperature under nitrogen for 24-48 hours. The reaction mixture isworked-up as in Example 3 to give a mixture of multidentate glycosides.Deacetylation as in Example 2 gives the polymer with sugar unitsattached to the alkyl polysulfide backbone. The degree of polymerizationis determined by chromatography on Sephadex gel.

                  TABLE 5                                                         ______________________________________                                         ##STR26##                                                                    Compound                                                                      no.      R'.sub.1                                                                             R'.sub.2                                                                             R'.sub.3                                                                           R'.sub.4                                                                             R'.sub.5                                                                             R'.sub.6                            ______________________________________                                        R = S(CH.sub.2).sub.15 CH.sub.3                                               ARSC16-1 OAc    H      OAc  OAc    H      H                                   ARSC16-2 OAc    H      OAc  OAc    H      CH.sub.2 OAc                        ARSC16-3 OAc    H      OAc  GalAcβ                                                                          H      CH.sub.2 OAc                        ARSC16-4 OAc    H      OAc  H      GalAcα                                                                         CH.sub.2 OAc                        R = S(CH.sub.2).sub.2 COOCH.sub.3                                             ARSC2E-1 OAc    H      OAc  GalAcβ                                                                          H      CH.sub.2 OAc                        ARSC2E-2 OAc    H      OAc  H      GalAcα                                                                         CH.sub.2 OAc                        ARSC2E-3 OH     H      OH   H      GalAcα                                                                         CH.sub.2 OH                         R = S(CH.sub.2).sub.10 COOCH.sub.3                                            ARSC10E-1                                                                              OAc    H      OAc  GalAcβ                                                                          H      CH.sub.2 OAc                        ARSC10E-2                                                                              OAc    H      OAc  H      GalAcα                                                                         CH.sub.2 OAc                        R = S(CH.sub.2).sub.3 SiO.sub.2                                               ARSC3-SiO.sub.2                                                                        OH     H      OH   GalOHβ                                                                          H      CH.sub.2 OH                         ______________________________________                                    

EXAMPLE 7 Formation of liquid crystals in dimethylsulfoxide

A bis-sulfide glycolipid (RSC16-8, RSC16-9, or RSC16-12; 5-10 mg) wasdissolved by gentle heating in dimethylsulfoxide (1 ml). When thetemperature had dropped to 30°-35° C., the still transparent mixturebecame semi-solid. Inspection of the mixture with a polarisingmicroscope revealed that liquid crystals had formed, preferentially inthe vicinity of entrapped bubbles of air. When the mixture was left forseveral hours, more stable aggregates (probably crystals) were formed asa precipitate and the remaining liquid became fluid.

EXAMPLE 8 Assay for virus binding specificity and estimation of relativebinding strength (a) Thin-layer plate method

The assay for the detection of virus binding to glycolipids and fortesting of detailed specificity of binding is of decisive importance(cf. (Hansson et al., FEBS Lett. 170, 1984, pp. 15-18). In principle,the virus to be assayed is layered on a chromatogram with separatedglycolipids from target cells or other sources and allowed to interactwith potential receptor substances. After careful washings, bound virusis detected by anti-virus antibody and radiolabelled anti-antibodyfollowed by autoradiography. In some cases, the virus particle wasdirectly labelled before binding. The detailed procedure is as follows:Mixtures of total lipids (up to 100 μg in each lane) or totalglycolipids (20-40 μg in each lane) or pure glycolipids (0.01-1 μg) wereseparated on aluminium sheets, about 5×5 cm, coated with silica gel 60(Merck), usually with chloroform/methanol/water (60:35:8, by volume) asthe solvent for non-acid glycolipids, and with chloroform/methanol/2.5Mammonia for non-acid glycolipids, and with chloroform/-methanol/2.5Mammonia (60:40:9, by volume) as the solvent for acid glycolipids. Forpurposes of comparison, a parallel plate is detected chemically byspraying and heating with anisaldehyde solution. For virus binding, thedried chromatogram with separated substances is dipped for 1 minute in200 ml of diethylether containing 0.5% (w/v) of polyisobutylmethacrylate(Plexigum P28, Rohm GmbH, Darmstadt) and dried for 2 minutes. The plateis then sprayed with phosphate-buffered saline (PBS) of pH 7.3containing 2% bovine serum albumin (BSA) and 0.1% NaN₃ (solution A) andthen immersed in solution A and placed in a Petri dish for 2 hours.After tipping off solution A, the virus suspension is added (about 25 μgper ml with about 2 ml for a plate of the dimensions given above) to thechromatogram placed horizontally in the humidified atmosphere of a Petridish. After incubation for 2 hours, the virus suspension is tipped offand the plate is washed six times with PBS, 1 minute each time. In atypical case of antibody, monoclonal antibody 817 directed againstSendai virus produced in ascitic fluid is diluted 1:100 with solution A,using about 2 ml per plate, with incubation for 2 hours. After washingfive times with PBS, about 2 ml of rabbit anti-mouse Fab is incubatedfor 2 hours (4×10⁵ cpm/ml of ¹²⁵ l-labelled F(ab')₂, the RadiochemicalCentre, Amersham). After six washings in PBS, the plate is dried andexposed to XAR-5 X-ray film (Eastman), usually for 2-3 days, using anintensifying screen.

The treatment with plastic produces a hydrophobic surface. Separatedglycolipid or other bands are thus induced to be exposed on thehydrophobic solid surface similar to the way lipids are exposed in thebiological membrane. This means that the test substance is denselyanchored with its paraffin chains in the plastic surface with the polarhead groups exposed and accessible to the invironment. This mimics thesurface monolayer of the living cell. This plastic treatment is highlycritical for specificity and reproducibility and explains the advantageof this solid-phase method over traditional inhibition assays based on"solubilized" aggregates or micelles.

The detection limit varies with the avidity of the ligand but is in therange of 5-50 ng of receptor, or in about the same picomole range. For areceptor candidate to be considered negative, there should be nodarkening at a one or more microgram level. Good binders give saturatingblack bands at 10 ng. An obvious advantage of this assay is thatmixtures or substances are first separated into substance species,avoiding the risk of shielding of minor components, or false negativebinding due to contaminating substance. Also, the coating with albuminblocks unspecific hydrophobic sites, which otherwise may cause falsepositive results. Finally, the extensive washings remove or detachunspecific associations. By comparison, traditional inhibition assaysusually incubate virus with target cells in suspension in the absence orpresence of sonicated micelles. In case of hemolysis assay, simplephotometry is done on the mixture after centrifugation (cf. Huang,Lipids 18, 1983, pp. 489-492 ). Thus, no albumin is present, and thereare no washing steps analogous to the present assay.

(b) Quantitation of virus binding by autoradiography of microtiterwells.

For quantification of virus binding, a technique was adopted from theanalogous solid-phase binding of antibodies to microtiter wells(Brockhaus et al., J. Biol. Chem. 256, 1981, pp. 13223-13225). Adilution series of glycolipid or other substances in 50 μl of methanolis allowed to evaporate in the microtiter well overnight at roomtemperature. 100 μl of 2% BSA in PBS are then incubated for 2 hoursafter which the well is rinsed once with the same volume of solution. 50μl of a suspension of 1.5 μg of virus in BSA-PBS is incubated for 4hours, followed by four washings with 100 μl each of BSA-PBS. In case ofSendai virus, 50 μl of ascitic fluid-produced antibody 817 diluted 1:100in solution A is incubated for 4 hours followed by four washings.Finally, 50 μl of rabbit anti-mouse Fab (2.5×10⁴ cpm ¹²⁵ l-labelledF(ab')₂, the Radiochemical Centre, Amersham) is incubated overnight at4° C. followed by five 100 μl washings with BSA-PBS. The wells are cutfrom the plate and assayed individually for ¹²⁵ l in a spectrometer. Theprocedure above was used to study the binding of Sendai virus to thesynthetic glycolipid analogues of the present invention. The compoundsof the invention studied were Glcβ→OCH₂ CH(CH₂ SO₂ (CH₂)₁₅ CH₃)₂(compound A) and Galβ1→4Glcβ→OCH₂ CH(CH₂ SO₂ (CH₂)₁₅ CH₃)₂ (compound B)in comparison with two natural receptors, viz. Galβ→Ceramide andGlcβ→Ceramide.

Semiquantitatively, compound A and compound B both showed excellentability to bind the virus. More quantitatively, compound b showedapproximately the same binding capacity as the natural comparisonreceptors. See also Table 6 below.

                                      TABLE 6                                     __________________________________________________________________________    Binding of Sendai virus to natural and synthetic glycolipids                  Glycolipid               Method    Result                                     __________________________________________________________________________    GlcβO--CH.sub.2 CH(CH.sub.2 S(CH.sub.2).sub.15 CH.sub.3).sub.2                                    TLC (Ex. 8a)                                                                            (+)                                        GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).sub.15 CH.sub.3).sub.    2                        TLC (Ex. 8a)                                                                            +                                          GlcβO--(CH.sub.2).sub.2 SO.sub.2 SO.sub.2 (CH.sub.2).sub.15 CH.sub.3                              TLC (Ex. 8a)                                                                            +                                          GalβO-ceramide      Autorad. MT-wells                                                                       +                                                                   (Ex. 8b)                                             GlcβO-ceramide      Autorad. MT-wells                                                                       +                                                                   (Ex. 8b)                                             GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).sub.15 CH.sub.3).sub.    2                        Autorad. MT-wells                                                                       +                                                                   (Ex. 8b)                                             Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).    sub.15 CH.sub.3).sub.2   Autorad. MT-wells                                                                       +                                                                   (Ex. 8b)                                             __________________________________________________________________________

(c) Quantitation of virus binding by ELISA method

Microtiter plates type Cooks M29 were used throughout thisinvestigation. Coating of the plates with natural glycolipids, syntheticglycolipids, and rabbit anti-Sendai virus-serum was performed in thefollowing manner:

Natural globotetraosyl-β-ceramide and galactosyl-β-ceramide weredissolved in analtical grade methanol to the following concentrations:20, 10, 5, 2.5, 1.5, 0.75, 0.375, 0.185, 0.092 and 0.046 μg/ml.Synthetic Galβ1→4GlcβO-CH₂ CH(CH₂ SO₂ (CH₂)₁₅ CH₃)₂,

GlcβO-CH₂ CH(CH₂ SO₂ (CH₂)₁₅ CH₃)₂, Galβ1→4Glcβ1→4GlcβO-CH₂ CH(CH₂S-(CH₂)₁₅ CH₃)₂, and GlcβO-CH₂ CH(CH₂ S(CH₂)₁₅ CH₃)₂ were dissolved inanalytical grade methanol to the following concentrations: 100, 50, 25,6.25, and 1.56 μg/ml. Each of the above solutions (50 μl) were added toa microtiter well and the methanol was allowed to evaporate over night.

Rabbit anti-Sendai virus-serum was diluted to 50 μg of protein/ml insodium carbonate/sodium hydrogen carbonate buffer to pH 9.6. The serumsolution (100 μl) was added to a series of microtiter wells andincubated at room temperature over night and the buffer solution wasremoved. A solution of BSA (100 μl, 2%) in Tris-HCl (5 mM)-NaCl (0.15M)solution (pH 8.5) was added. The plates were incubated at 37° C. for 2 hand then washed twice with an excess of BSA-solution (1%) in Tris-HCl(50 mM)-NaCl (0.15M) having pH 8.5.

Sendai virus was diluted to a protein concentration of 15 μg/ml in asolution of BSA (1%) in Tris-HCl (50 mM)-NaCl (0.15M), pH 8.5. The virussolution (100 μl) was added to each coated well of the above mentionedmicrotiter plates. The plates were incubated at 37° C. for 2 h and thenwashed four times with an excess of BSA-solution (1%) in Tris-HCl-NaCl(concentration as above). Mouse monoclonal anti-Sendai virus antibody inBSA-solution (100 μl, 1% of BSA, Tris-HCl-NaCl as above), was added toeach well. The plates were incubated at 37° C. for 90 min. and thenwashed four times with an excess of BSA-solution (1% of BSA inTris-HCl-NaCl as above). Horseradish peroxidase-conjugated rabbitanti-mouse antibody (Dakopatts) was diluted to 20 μg/ml in BSA-solution(1% of BSA, Tris-HCl-NaCl as above). Aliquots (100 μl) were added to themicrotiter wells above and the plates were incubated at 37° C. for 90min. and then washed four times with an excess of BSA-solution (1% ofBSA, Tris-HCl-NaCl as above). Orthophenylenediamine (OPD) solution (100μl; 4 mg OPD and 4 μl 30 % H₂ O₂ in 10 ml of 0.1M citrate phosphatebuffer; pH 5.0) was added to each well and the plates were incubated atroom temperature for 15 min. Sulfuric acid (50 μl, 0.5M) was added toeach well and the absorption was measured at 492 nm (see FIG. 1).

(d) Inhibition of virus binding; ELISA method

This assay was performed as described above (c) with the followingexceptions:

(1) Only one concentration (10 μg/ml) of globotetraosyl-β-ceramide andgalactosyl-β-ceramide was used.

(2) Before addition of virus suspension to the microtiter wells, thevirus was incubated with varying amounts of the neo-glycoprotein[Galβ1→4GlcβO-CH₂ CH(CH₂ SO₂ (CH₂)₇ CH₃)CH₂ SO₂ (CH₂)₁₀ COONH].sub.˜20-BSA. The noe-glycoprotein was dissolve in Tris-HCl (50 mM)-NaCl(0.15M), pH 8.5 to the following concentrations: 4.4, 1.1, 0.275, 0.069,0.017, 0.004, and 0.001 mg/ml. Sendai virus suspension (4 μl) was addedto each of the neo-glycoprotein solutions (265 μl) so that the finalvirus concentration was 45 μg/ml. The mixture was incubated at 37° C.for 2 h and the resulting virusneoglycoprotein-suspension (50 μl) wasused in the virus assay as described above (c). The results are shown inFIG. 2. Globotetraosyl-β-ceramide was used as a negative control sinceit has been shown earlier to lack binding capacity of Sendai virus.

(e) Inhibition of virus binding; thin-layer plate method

Sendai virus (60 μg) was incubated at room temperature for 1 h withGalβ1→4GlcβO-CH₂ CH(CH₂ SO₂ -(CH₂)₁₀ COONa)₂ (2 mg), Galβ1→4Glcβ-O-CH₂CH(CH₂ SO₂ (CH₂)₇ CH₃ (CH₂ SO₂ (CH₂)_(h19) COONa (2 mg), andGalβ1→4GlcβO-CH₂ CH(CH₂ SO₂ (CH₂)₇ CH₃)CH₂ SO₂ (CH₂)₁₀ CONH-BSA (1 mg),each dissolved in 2 ml of PBS. The mixtures were overalid on thin layerplates containing several natural glycolipids known as second stepreceptors for Sendai virus (see Karl-Anders Karlsson, Antiviral agents;Danish patent application No. 178/85 filed on the priority date of thepresent application). The plates were incubated and worked up asdescribed above (Ex. 8a). A positive inhibition was registered as asignificant weakening of the darkness of receptor spots on theautoradiogram. The results are shown in Table 7 below.

                                      TABLE 7                                     __________________________________________________________________________    Inhibition of Sendai virus binding to natural glycolipids by synthetic        neo-glycoconjugates.                                                          Neo-glycoconjugate                   Inhibition                               __________________________________________________________________________    Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).    sub.10 COONa).sub.2                  -                                        Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).    sub.7 CH.sub.3)CH.sub.2 SO.sub.2 (CH.sub.2).sub.10 COONa                                                           -                                        Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 SO.sub.2 (CH.sub.2).    sub.7 CH.sub.3)CH.sub.2 SO.sub.2 (CH.sub.2).sub.10 CONHBSA                                                         +                                        __________________________________________________________________________

EXAMPLE 9 Assay for bacterial binding specificity; thin layer platemethod

The method has been described in detail (Hansson et al., Anal. Biochem.146, 1985, pp. 158-163). Bacteria were externally radiolabelled usinglodogen and Na¹²⁵ l (Hansson et al. above). E. Coli was the straincharacterized in detail elsewhere for Galα→Gal binding specificity (Bocket al. J. Biol. Chem. 260, 1985, pp 8545-8551). Propionibacteriumfreudenreichii has been reported earlier to bind lactosylceramid(Hansson et al., Glycoconjugates, M. A. Chester, D. Heinegard, A.Lundblad and S. Svensson, eds. 1983, pp 631-632, Rahms in Lund, Lund,Sweden). The radiolabelled bacteria were over-layed on plates thatcontained the neo-glycolipids shown in Table 8 below. Work-up anddetection was performed as described in the references above(essentially as for virus binding as described in Example 8a). Theresults are shown in Table 8 below.

                                      TABLE 8                                     __________________________________________________________________________    Binding of bacteria to synthetic glycolipids                                  Glycolipid                 Bacterium                                                                             Binding                                    __________________________________________________________________________    Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 --S--(CH.sub.2).sub.    15 CH.sub.2).sub.2         Propionibacterium                                                                     (+)                                                                   freudenreichii                                     Galβ1 → 4GlcβO--CH.sub.2 CH(CH--S--(CH.sub.2).sub.17         CH.sub.3).sub.2            "       (+)                                        Galβ1 → 4GlcβO--CH.sub.2 CH(CH.sub.2 -- SO.sub.2             --(CH.sub.2).sub.15 CH.sub.3).sub.2                                                                      "       +                                          Galα1 → 4GalβO--CH.sub.2 CH(CH.sub.2 --S--(CH.sub.2).sub    .15 CH.sub.3).sub.2        E. coli +                                          Galα1 → 4GalβO--CH.sub.2 CH(CH.sub.2 --SO.sub.2             --(CH.sub.2).sub.15 CH.sub.3).sub.2                                                                      "       +                                          __________________________________________________________________________

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We claim:
 1. An O-glycosidic compound of the formula (sugar)_(n)-1-O-CH₂ -A where A is ##STR27## B_(x) and B_(y), which may be the sameor different, are groups of the formula II, ##STR28## n is an integerfrom 1 to 10, inclusive, and sugar is selected from the group consistingof D-glucose, D-galactose, D-mannose, D-xylose, D-ribose, D-arabinose,L-fucose, 2-acetamido-2-deoxy-D-glucose,2-acetamido-2-deoxy-D-galactose, D-glucuronic acid, D-galacturonic acid,D-mannuronic acid, 2-deoxy-2-phthalimido-D-glucose,2-deoxy-2-phthalimido-D-galactose and sialic acid, and derivativesthereof, where, when n>1, the sugar units may be the same ordifferent,where m and p independently are 0 or 1 and m+p is 0, 1, or 2,R₄ is a saturated or unsaturated, branched or unbranched chain of 1-25carbon atoms, aryl or a steroid group, R₅ is H, CHO, NO₂, NH₂, OH, SH,COOH, COOR₁₀, CONHNH₂, CON₃, CH(OR₁₀)₂, or a carrier, and R₁₀ is C₁₋₄alkyl or a carrier.
 2. The compound of claim 1 where A is --C(═CH₂)-Bx.3. The compound of claim 2 wherein m=0 and p=0.
 4. The compound of claim1 where A is: ##STR29##
 5. The compound of claim 4 wherein m=0 and p=0.6. The compound of claim 4 wherein m=1 and p=0.
 7. The compound of claim4 wherein m=1 and p=1.
 8. The compound of claim 1 wherein the compoundbinds preferentially to a virus.
 9. The compound of claim 8 wherein thecompounds binds to Sendai virus.
 10. The compound of claim 1 wherein thecompound competitively inhibits the binding of a virus to a naturalglycolipid membrane receptor.
 11. The compound of claim 1 wherein thecompound binds preferentially to a bacterium.
 12. The compound of claim1 wherein the compound binds to Proprionibacterium freudenreichii orEsherichia coli.
 13. The compound of claim 1 in which R₄ is anunbranched alkyl chain of 2-17 carbon atoms and R₅ is H, COOR₁₀ whereinR₁₀ is CH₃ or a carrier.
 14. The compound of claim 1 in which m=0 andp=0.
 15. The compound of claim 1 in which m=1 and p=0.
 16. The compoundof claim 1 in which m=1 and p=1.
 17. The compound of claim 5 wherein thecompound is selected from the group consisting of RSC16-1, RSC16-2,RSC16-3, RSC16-4, RSC16-5, RSC16-6, RSC16-7, RSC16-8, RSC16-9, RSC16-10,RSC16-11, RSC16-12, RSC16-13, RSC16-14, RSC18-1, RSC8-1, RSC8-2,RSC10E-1, RSC10E-2, and RSC10EC8 as defined in Table
 2. 18. The compoundof claim 6 wherein the compound is selected from the group consisting ofRSOC16-1, RSOC16-2, RSOC16-3, RSOC16-4, RSOC16-5, RSOC16-6, RSOC16-7,RSOC16-8, RSOC16-9, RSOC16-10, RSOC16-11, RSOC16-12, RSOC16-13,RSOC16-14, ROSC18-1, RSOC18-2, RSOC8-1, ROSC8-2, RSOC10E-1, andRSOC10E-2 as defined in Table
 3. 19. The compound of claim 7 wherein thecompound is selected from the group consisting of RSO₂ C16-1, RSO₂C16-2, RSO₂ C16-3, RSO₂ C16-4, RSO₂ C16-5, RSO₂ C16-6, RSO₂ C16-7, RSO₂C16-8, RSO₂ C16-9, RSO₂ C16-10, RSO₂ C16-11, RSO₂ C16-12, RSO₂ C16-13,RSO₂ C16-14, RSO₂ C18-1, RSO₂ C18-2, RSO₂ C8-1, ROS₂ C8-2, RSO₂ C10E-1,RSO₂ C10E-2, RSO₂ C10A, RSO₂ C10EC8-1, RSO₂ C10EC8-2 and RSO₂ C10AC8 asdefined in Table
 4. 20. The compound of claim 3 wherein the compound isselected from the group consisting of ARSC16-1, ARSC16-2, .
 21. Apolymeric compound having the formula XX ##STR30## where k is an integerfrom 2-1000, n is 1-10, and sugar is selected from the group consistingof D-glucose, D-galactose, D-mannose, D-xylose, D-ribose, D-arabinose,L-fucose, 2-acetamido-2-deoxy-D-glucose,2-acetamido-2-deoxy-D-galactose, D-glucuronic acid, D-galacturonic acid,D-mannuronic acid, 2-deoxy-2-phthalimido-D-glucose,2-deoxy-2-phthalimido-D-galactose and sialic acid, and derivativesthereof, where, when n>1, the sugar units may be the same or different,and R₄ is a saturated or unsaturated, branched or unbranched chain of1-25 carbon atoms, aryl or a steroid group.
 22. A polymeric compoundcomprising a three-dimensional network of 2-1000 units of the formulaXXIa ##STR31## and 2-1000 units of the formula XXIb, ##STR32## wherein aunit of Formula XXIa is never bonded directly to another unit of FormulaXXIa and a unit of Formula XXIb is never bonded directly to another unitof Formula XXIb,R₄ is a saturated or unsaturated, branched or unbranchedchain of 1-25 carbon atoms, aryl or a steroid group, n=1 to 10, andsugar is selected from the group consisting of D-glucose, D-galactose,D-mannose, D-xylose, D-ribose, D-arabinose, L-fucose,2-acetamido-2-deoxy-D-glucose, 2-acetamido-2-deoxy-D-galatose,D-glucuronic acid, D-galacturonic acid, D-mannuronic acid,2-deoxy-2-phthalimido-D-glucose, 2-deoxy-2-phthalimido-D-galactose andsialic acid, and derivatives thereof, where, when n>1, the sugar unitsmay be the same or different.
 23. The compound of claim 1 wherein thesteroid is cholesterol or lanosterol.
 24. The compound of claim 1wherein n>1.
 25. The compound of claim 1 in which (a) R₅ is a carrier,or (b) R₅ is --COOR₁₀ or --CH(OR₁₀)₂, and R₁₀ is a carrier.
 26. AnO-glycosidic compound of the formula (sugar)_(n) -1-O-CH₂ -A, where A is##STR33## and R₁ is a group of the Formula II, ##STR34## and R₂ is agroup of formula II, a group -CH₂ X wherein X is a leaving group, agroup -CH₂ OR₆ (wherein R₆ is -H or -R₄ -R₅), or a group ##STR35##wherein R₇ and R'₇ which may be same or different, are the same as R₆defined above, n is an integer from 1 to 10, inclusive, and sugar isselected from the group consisting of D-glucose, D-galactose, D-mannose,D-xylose, D-ribose, D-arabinose, L-fucose,2-acetamido-2-deoxy-D-glucose, 2-acetamido-2-deoxy-D-galactose,D-glucuronic acid, D-galacturonic acid, D-mannuronic acid,2-deoxy-2-phthalimido-D-glucose, 2-deoxy-2-phthalimido-D-galactose andsialic acid, and derivatives thereof, where, when n>1, the sugar unitsmay be the same or different,where m and p independently are 0 or 1 andm+p is 0, 1, or 2, R₄ is saturated or unsaturated, branched orunbranched chain of 1-25 carbon atoms, aryl or a steroid group, R₅ is H,CHO, NO₂, NH₂, OH, SH, COOH, COO_(R10), CONHNH₂, CON₃, CH(OR₁₀)₂, or acarrier, and R₁₀ is C₁₋₄ alkyl or a carrier.
 27. An O-glycosidiccompounds of the formula I(b), (sugar)_(n) -1-O-C(═CH₂)-CH₂ X, where Xis a halogen, n=1 to 10 inclusive, and sugar is selected from the groupconsisting of D-glucose, D-galactose, D-mannose, D-xylose, D-ribose,D-arabinose, L-fucose, 2-acetamido-2-deoxy-D-glucose,2-acetamido-2-deoxy-D-galactose, D-glucuronic acid, D-galacturonic acid,D-mannuronic acid, 2-deoxy-2-phthalimido-D-glucose,2-deoxy-2-phthalimido-D-galactose and sialic acid, and derivativesthereof, where, when n>1, the sugar units may be the same or different.